Process for recording on optical recording medium

ABSTRACT

An optical recording medium comprising a substrate and a thin organic film containing at least one kind of dye selected from polymethine family dyes, perylium family dyes, and cyanine family dyes, and a recording process comprising scanning the optical recording medium with a high intensity light beam such as a laser beam to form optically detectable pits on the recording medium.

This application is a division of application Ser. No. 07/512,587, filedApr. 24,1990, now U.S. Pat. No. 5,678,127, which in turn, is a divisionof application Ser. No. 378,491, filed Jul. 11, 1989, now abandoned;which in turn, is a continuation of application Ser. No. 053,563, filedMay 21, 1987, now abandoned; which in turn, is a continuation ofapplication Ser. No. 756,570, filed Jul. 18, 1985, now abandoned; whichin turn, is a continuation of application Ser. No. 481,741, filed Apr.4, 1983, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to an optical recording medium suited for writinga record with a laser, especially with a semiconductor laser, and moreparticularly to an improved optical recording medium used in the art ofoptical disk.

2. Description of the Prior Art

The optical disk comprises generally a circular substrate overlaid witha thin recording layer, on which high density information can be storedin the form of spiral or circular track of minute, optically detectablepits (e.g. about 1 μ size). For writing information on such a disk, alaser-responsive layer, i.e. the thin recording layer, is scannedspirally or circularly with a convergent laser beam to form pits on thetrack of the scanning laser beam. The laser-responsive layer can formoptically detectable pits by absorbing laser energy. In a heat moderecording system, for instance, the laser-responsive layer can absorbthermal energy of a laser beam and form minute pits at irradiated spotsthrough evaporation or melting. In another heat mode recording system,pits having an optically detectable difference of optical density can beformed on spots wherein laser energy is absorbed.

The information recorded on the optical disk can be scanned along thetrack of pits with a laser to read out optical variations due to thepresence and absence of pit. For instance, the energy of the readinglaser reflected from the disk is monitored with a photodetector. Whenfalling on the pit-free area, an output of the photodetector is lowered.On the contrary, when irradiating a pit, the laser is adequatelyreflected from an underlying reflecting surface, giving a highphotodetector output.

In the past, various films were proposed as recording media to be usedfor these optical disks. Such films are chiefly inorganic materialsincluding thin films of metals such as vacuum-deposited aluminum, thinfilms of bismuth and of tellurium oxide, and amorphous glass films ofchalcogenite group. Generally, these films are responsive to rays ofabout 350-800 nm in wavelength and have high reflectance for laserbeams, thus involving drawbacks such as a low efficiency of laser energyutilization.

For this reason and others, extensive studies have been made in recentyears on organic thin films capable of altering some optical propertiesby irradiation with relatively long wavelength light (longer than about780 nm). Such organic thin films are effective in that pits can beformed therein by means of a semiconductor laser of wavelength, forexample, around 830 nm.

However, organic compounds having absorption maxima in a longerwavelength region are generally unstable to heat and additionally havesome technical difficulties with respect to their sublimation property.Such being the case, it cannot be said that an organic thin filmsatisfactory in performance characteristics has been developed.

SUMMARY OF THE INVENTION

An object of this invention is to provide an optical recording mediumand a process for making a record thereupon, said recording mediumhaving an organic thin film capable of absorbing rays of longerwavelengths.

Another object of this invention is to provide an optical recordingmedium and a process for making a record thereupon, said recordingmedium having an organic thin film stable to heat.

These objects of this invention can be achieved with an opticalrecording medium comprising a substrate and an organic thin filmcontaining at least one of the compounds severally represented by thefollowing formulae (1)-(10). ##STR1##

In Formula (1), R₁₁ and R₁₂ each represent alkyl, substituted alkyl,cyclic alkyl, alkenyl, aralkyl, substituted aralkyl, aryl, orsubstituted aryl; Z₁₁ and Z₁₂ each represent a nonmetal atomic groupnecessary to complete a substituted or unsubstituted heterocyclic ring;a and b are each 0 or 1; M.sup.⊕ represents a cation; and X.sup.⊖represents an anion. ##STR2##

In Formula (2), R₁₁ and R₁₂ each represent alkyl, substituted alkyl,cyclic alkyl, alkenyl, aralkyl, substituted aralkyl, aryl, orsubstituted aryl; Z₁₁ and Z₁₂ each represent a nonmetal atomic groupnecessary to complete a substituted or unsubstituted heterocyclic ring;and a and b are each 0 or 1. ##STR3##

In formula (3), Z₃₂ represents sulfur, oxygen, or selenium;

Z₃₁ represents a hydrocarbon residue necessary to complete a pyrylium,thiapyrylium, selenopyrylium, benzopyrylium, benzothiapyrylium,benzoselenopyrylium, naphthopyrylium, naphthothiapyrylium, ornaphthoselenopyrylium ring which may be substituted or not;

R₃₁ and R₃₂ each represent hydrogen or a substituted or unsubstitutedalkyl, aryl, or styryl residue;

R₃₃ represents a substituted or unsubstituted aryl or heterocyclicresidue;

R₃₄ and R₃₅ each represent hydrogen or alkyl;

X.sup.⊖ represents an anion;

d is 1 or 2;

e is 0, 1, or 2; wherein when e is 2, the two R₃₄ are the same ordifferent and the two R₃₅ are the same or different. ##STR4##

In Formula (4), Z₄₃ and Z₄₄ each represent sulfur oxygen, or selenium;

Z₄₁ represents a hydrocarbon residue necessary to complete a pyrylium,thiapyrylium, selenapyrylium, benzopyrylium, benzothiapyrylium,benzoselenapyrylium, naphthopyrylium, naphthothiopyrylium, ornaphthoselenopyrylium ring which may be substituted or not;

Z₄₂ represents a hydrocarbon residue necessary to complete a pyrane,thiapyrane, selenapyrane, benzopyrane, benzothiapyrane,benzoselenapyrane, naphthopyrane, naphthothiapyrane, ornaphthiaselenopyrane ring which may be substituted or not;

R₄₁, R₄₂, R₄₃, and R₄₄ each represent hydrogen or a substituted orunsubstituted alkyl or aryl residue;

R₄₅, R₄₆, and R₄₇ each represent hydrogen, halogen, or a substituted orunsubstituted alkyl, aryl, or aralkyl residue;

X.sup.⊖ represents an anion;

f and h are each 1 or 2; and

g is 0, 1, or 2; wherein, when g is 2, the two R₄₅ are the same ordifferent and the two R₄₆ are the same or different. ##STR5##

In Formula (5), A, B, D, and E each represent aryl or substituted aryl;

R₅₁, R₅₂, R₅₃, R₅₄, and R₅₅ each represent hydrogen, halogen, or alkyl;

Y represents a divalent residue necessary to complete a 5- or 6-memberedring; and

X.sup.⊖ represents an anion. ##STR6##

In Formula (6), R₆₁, R₆₂, R₆₃, R₆₄, and R₆₅ each represent hydrogenalkyl, substituted alkyl, cyclic alkyl, alkenyl, aralkyl, substitutedaralkyl, aryl, substituted aryl, styryl, substituted styryl,heterocyclic, or substituted heterocyclic residue;

X.sup.⊖ represents an anion;

i is 0, or 1; and

j is 0, 1, or 2. ##STR7##

In Formula (7), Z₇₁ and Z₇₂ each represent an atomic group necessary tocomplete a nitrogen-containing heterocyclic ring substituted orunsubstituted;

A₁ and A₂ each represent a divalent hydrocarbon residue necessary tocomplete a substituted or unsubstituted 5- or 6-membered ring;

R₇₁ and R₇₂ each represent hydrogen, alkyl, substituted alkyl, cyclicalkyl, alkenyl, aralkyl, or substituted aralkyl;

R₇₃ and R₇₄ each represent hydrogen or halogen;

X.sup.⊖ represents an anion;

k and m are each 0 or 1; and

l is 1 or 2. ##STR8##

In Formula (8), Z₈₁ and Z₈₂ each represent an atomic group necessary tocomplete a nitrogen-containing heterocyclic ring substituted orunsubstituted;

Z₈₃ represents a divalent hydrocarbon residue necessary to complete a 5-or 6-membered ring;

R₈₁ and R₈₂ each represent hydrogen, alkyl, substituted alkyl, cyclicalkyl, alkenyl, aralkyl, or substituted aralkyl;

Q represents oxygen, sulfur, imino, substituted imino, or an organicdivalent residue;

s, t, and r are each 0 or 1; and

p and q are each 0, 1, or 2. ##STR9##

In Formula (1), A₃.sup.⊖ represents ##STR10##

Z₉₃ and Z₉₄ each represent sulfur, oxygen, or selenium;

Z₉₁ represents an atomic group necessary to complete a pyrylium,thiapyrylium, selenapyrylium, benzopyrylium, benzothiapyrylium,benzoselenapyrylium, naphthothiapyrylium, naphthothiapyrylium, ornaphthoselenapyrylium ring which may be substituted or not;

Z₉₂ represents an atomic group necessary to complete a pyrane,thiapyrane, selenapyrane, benzopyrane, benzothiapyrane,benzoselenapyrane, naphthopyrane, naphthothiapyrane, ornaphthoselenapyrane ring which may be substituted or not;

R₉₁ R₉₂ R₉₃, and R₉₄ each represent hydrogen, alkyl, alkoxyl, or asubstituted or unsubstituted aryl, styryl, 4-phenyl-1,3-butadienyl, orheterocyclic residue, where R₉₁ coupled with R₉₂ and R₉₃ coupled withR₉₄ can each form a substituted or unsubstituted benzene ring; and

v and w are each 1 or 2. ##STR11##

In Formula (10), R₂₁ and R₂₂ represent each alkyl, or R₂₁ and R₂₂together with the nitrogen atom to which they are attached form a ring;and

R₂₃, R₂₄, R₂₅, and R₂₆ each represent hydrogen, halogen, alkyl, alkoxy,or hydroxyl, where combinations of R₂₃ and R₂₄ and combinations of R₂₅and R₂₆ can form each a benzene ring.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 are absorption spectra of Compound Nos. I-(29) and IX-(1),respectively.

FIG. 3 is an absorption spectrum of Compound No. VIII-(7) coveringvisible and infrared ray wavelength regions.

FIGS. 4 and 5 are cross-sectional views of optical recording media ofthis invention.

FIG. 6 is an illustration showing an embodiment of the process formaking a record on the optical recording medium of this invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The optical recording medium of this invention is characterized byhaving an organic thin film that contains at least one of the dyesseverally represented by the foregoing general formulae (1)-(10).

Referring to these formulae, the symbols therein are illustrated belowin detail together with examples of the dyes represented by theformulae.

R₁₁ and R₁₂ in Formulae (1) and (2) each represent alkyl (e.g. methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl,n-amyl, t-amyl, n-hexyl, n-octyl, or t-octyl), substituted alkyl (e..g.2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl,carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 2-sulfoethyl,3-sulfopropyl, 4-sulfobutyl, 3-sulfatepropyl, 4-sulfatebutyl,N-(methylsulfonyl)-carbamylmethyl, 3-(acetylsulfamyl) propyl, or4-(acetylsulfamyl)butyl], cyclic alkyl (e.g. cyclohexyl), alkenyl [e.g.allyl (CH₂ ═CH--CH₂ --)), aralkyl (e.g. benzyl, phenethyl,3-phenylpropyl, α-naphthylmethyl, or β-naphthylmethyl), substitutedaralkyl (e.g. carboxybenzyl, sulfobenzyl, or hydroxybenzyl), aryl (e.g.phenyl) or substituted aryl (e.g. carboxyphenyl, sulfophenyl, orhydroxyphenyl). Of these organic residues, hydrophobic ones areparticularly preferable in this invention.

Z₁₁ and Z₁₂ each represent a nonmetal atomic group necessary to completea substituted or unsubstituted heterocyclic ring such as a thiazolefamily ring (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole,5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole,4,5-diphenylthiazole, or 4-(2-thienyl)thiazole), benzothiazole familyring (e.g. benzothiazole, 5-chlorobenzothiazole, 5-methylbenzothiazole,6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-bromobenzothiazole,5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole,5,6-dimethoxybenzothiazole, 5,6-di(hydroxymethyl)benzothiazole,5-hydroxybenzothiazole, 6-hydroxybenzothiazole, or4,5,6,7-tetrahydrobenzothiazole), naphthothiazole family ring (e.g.naphtho(2,1-d)thiazole, naphtho(1,2-d)thiazole,5-methoxynaphtho(1,2-d)thiazole, 5-ethoxynaphtho(1,2-d)thiazole,8-methoxynaphtho(2,1-d)thiazole, or 7-methoxynaphtho(2,1-d)thiazole),thionaphthene(7,6-d)thiazole family ring (e.g.7-methoxythionaphthene(7,6-d)thiazole), oxazole family ring (e.g.4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole,4-ethyloxazole, 4,5-dimethyloxazole, or 5-phenyloxazole), benzoxazolefamily ring (e.g. benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole,5-phenylbenzoxazole, 6-methylbenzoxazole, 5-6-dimethylbenzoxazole,5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, or6-hydroxybenzoxazole), naphthoxazole family ring (e.g.naphtho(2,1-d)oxazole or naphtho(1,2-d)oxazole), selenazole family ring(e.g. 4-methylselenazole or 4-phenylselenazole), benzoselenazole familyring (e.g. benzoselenazole, 5-chlorobenzoselenazole,5-methylbenzoselenazole, 5,6-dimethylbenzoselenazole,5-methoxybenzoselenazole, 5-methyl-6-methoxybenzoselenazole,5,6-di(hydroxymethyl)benzoselenazole, 5-hydroxybenzoselenazole, or4,5,6,7-tetrahydrobenzoselenazole), naphthoselenazole family ring (e.g.naphtho(2,1-d) selenazole or naphtho(1,2-d)selenazole), thiazolinefamily ring (e.g. thiazoline, 4-methylthiazoline,4-hydroxymethyl-4-methylthiazoline, or4,4-bis(hydroxymethyl)thiazoline), oxazoline family ring (e.g.oxazoline), selenazoline family ring (e.g. selenazoline), 2-quinolylfamily ring (e.g. quinoline, 6-methylquinoline, 6-chloroquinoline,6-methoxyquinoline, 6-ethoxyquinoline, or 6-hydroxyquinoline),4-quinolyl family ring (e.g. quinoline, 6-methoxyquinoline,7-methylquinoline, or 8-methylquinoline), 1-isoquinolyl family ring(e.g. isoquinoline or 3,4-dihydroxyisoquinoline), 3-isoquinolyl familyring (e.g. isoquinoline), 3,3-dialkylindolenine family ring (e.g.3,3-dimethylindolenine, 3,3-dimethyl-5-chloroindolenine,3,3,5-trimethylindolenine, or 3,3,7-trimethylindolenine), pyridinefamily ring (e.g. pyridine or 5-methylpyridine), or benzimidazole familyring (e.g. 1-ethyl-5,6-dichlorobenzimidazole,1-hydroxyethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole,1-ethyl-5,6-dibromobenzimidazole, 1-ethyl-5-phenylbenzimidazole,1-ethyl-5-fluorobenzimidazole, 1-ethyl-5-cyanobenzimidazole,1-(8-acetoxyethyl)-5-cyanobenzimidazole,1-ethyl-5-chloro-6-cyanobenzimidazole,1-ethyl-5-fluoro-6-cyanobenzimidazole, 1-ethyl-5-acetylbenzimidazole,1-ethyl-5-carboxybenzimidazole, 1-ethyl-5-ethoxycarbonylbenzimidazole,1-ethyl-5-sulfamylbenzimidazole, 1-ethyl-5-N-ethylsulfamylbenzimidazole,1-ethyl-5,6-difluorobenzimidazole, 1-ethyl-5,6-dicyanobenzimidazole,1-ethyl-5-ethylsulfonylbenzimidazole,1-ethyl-5-methylsulfonylbenzimidazole,1-ethyl-5-trifluoromethylbenzimidazole,1-ethyl-5-trifluoromethylsulfonylbenzimidazole, or1-ethyl-5-trifluoromethylsulfinylbenzimidazole).

In Formulae (1) and (2), a and b are each 0 or 1.

In Formula (1), X.sup.⊖ represents an anion (e.g. chloride, bromide,iodide, perchlorate, benzenesulfonate, p-toluenesulfonate,methylsulfate, ethylsulfate, or propylsulfate anion). However, X.sup.⊖is not contained in the formula when R₁₁ and/or R₁₂ itself has an anion(e.g. --SO₃.sup.⊖, --OSO₃.sup.⊖, --COO.sup.⊖, --HNSO₂.sup.⊖, --SO₂--N.sup.⊖ --CO--, or --SO₂ --N.sup.⊖ --SO₂ --). M.sup.⊖ represents acation (e.g. proton, sodium ion, ammonium ion, potassium ion, orpyridinium ion).

Among the croconic methine dyes represented by Formula (1) or (2),preferred ones are enumerated below. For convenience, structuralformulae thereof are expressed in betaine form, though these dyes aregenerally obtained and used, as mixtures of betaine and salt forms.

    __________________________________________________________________________    Croconi methine dyes                                                          Compound No.                                                                          Chemical Formula                                                      __________________________________________________________________________    I-(1)                                                                                  ##STR12##                                                            I-(2)                                                                                  ##STR13##                                                            I-(3)                                                                                  ##STR14##                                                            I-(4)                                                                                  ##STR15##                                                            I-(5)                                                                                  ##STR16##                                                            I-(6)                                                                                  ##STR17##                                                            I-(7)                                                                                  ##STR18##                                                            I-(8)                                                                                  ##STR19##                                                            I-(9)                                                                                  ##STR20##                                                            I-(10)                                                                                 ##STR21##                                                            I-(11)                                                                                 ##STR22##                                                            I-(12)                                                                                 ##STR23##                                                            I-(13)                                                                                 ##STR24##                                                            I-(14)                                                                                 ##STR25##                                                            I-(15)                                                                                 ##STR26##                                                            I-(16)                                                                                 ##STR27##                                                            I-(17)                                                                                 ##STR28##                                                            I-(18)                                                                                 ##STR29##                                                            I-(19)                                                                                 ##STR30##                                                            I-(20)                                                                                 ##STR31##                                                            I-(21)                                                                                 ##STR32##                                                            I-(22)                                                                                 ##STR33##                                                            I-(23)                                                                                 ##STR34##                                                            I-(24)                                                                                 ##STR35##                                                            I-(25)                                                                                 ##STR36##                                                            I-(26)                                                                                 ##STR37##                                                            I-(27)                                                                                 ##STR38##                                                            I-(28)                                                                                 ##STR39##                                                            I-(29)                                                                                 ##STR40##                                                            I-(30)                                                                                 ##STR41##                                                            I-(31)                                                                                 ##STR42##                                                            I-(32)                                                                                 ##STR43##                                                            I-(33)                                                                                 ##STR44##                                                            I-(34)                                                                                 ##STR45##                                                            __________________________________________________________________________

The dyes can be used in this invention separately or in combination.

As described in Japanese Patent Publication No. 41061/1976, thesecroconic methine dyes can be prepared, for instance, by condensation ofcroconic acid or its derivative (e.g. mono- or dialkyl croconate) with2-methyl-cyclo quaternary ammonium salt, which is well known in thechemistry of cyanine dyes, or with the 2-methylene base correspondingthereto.

The preparation of a typical croconic methine dye used in this inventionis illustrated by the following Preparation Example:

PREPARATION EXAMPLE 1 Synthesis of the above-cited compound No. I-(29)

A mixture of 1.20 g (0.00845 mole) of croconic acid, 5.06 g (0.0169mole) of quinaldine ethiodide, and 50 ml of n-butanol was heated up to110° C., and, by adding 4 ml of pyridine, was reacted at 110°-116° C.for 10 minutes. After addition of 4 ml of triethylamine and stirring atthe same temperature for 5 minutes, the mixture was allowed to stand toprecipitate a dye, which was then filtered off, washed with n-butanoland successively with tetrahydrofuran, and dried under reduced pressure.Thus, 2.1 g (yield 55%) of a purified dye was obtained. The absorptionspectrum of this dye in dimethylsulfoxide is shown in FIG. 1 (λmax=845nm).

In Formula (3), Z₃₂ represents sulfur, oxygen., or selenium, and Z₃₁represents a hydrocarbon residue necessary to complete a pyrylium,thiapyrylium, selenapyrylium, benzopyrylium, benzothiapyrylium,benzoselenapyrylium, naphthopyrylium, naphthothiapyrylium, ornaphthoselenapyrylium ring which may be substituted or not. Suitablesubstituents on the ring include halogens such as chlorine, bromine, andfluorine; alkyls such as methyl, ethyl, propyl, isopropyl, butyl,t-butyl, amyl, isoamyl, hexyl, octyl, nonyl, and dodecyl; aryls such asphenyl, α-naphthyl, and β-naphthyl; substituted aryls such as tolyl,xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,amyloxyphenyl, dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl,chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl,diethylaminophenyl, dimethylaminophenyl, and dibenzylaminophenyl;styryl; and substituted styryls such as chlorostyryl,dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl,dibutylaminostyryl, dibenzylaminostyryl, diphenylaminostyryl,methoxystyryl, and ethoxystyryl.

R₃₁ and R₃₂ each represent hydrogen; alkyl particularly a C₁ -C₁₅ alkyl(e.g. methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl, isoamyl,hexyl, octyl, nonyl, or dodecyl); aryl (e.g. phenyl, α-naphthyl, orβ-naphthyl); substituted aryl (e.g. tolyl, xylyl, biphenyl, ethylphenyl,methoxyphenyl, ethoxyphenyl, amyloxyphenyl, dimethoxyphenyl,diethoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl,bromophenyl, dibromophenyl, nitrophenyl, diethylaminophenyl,dimethylaminophenyl, or dibenzylaminophenyl); styryl; or substitutedstyryl (e.g. chlorostyryl, dichlorostyryl, methylstyryl, dimethylstyryl,methoxystyryl, ethoxystyryl, dimethylaminostyryl, diethylaminostyryl,dipropylaminostyryl, dibutylaminostyryl, dibenzylaminostyryl, ordiphenylaminostyryl).

R₃₃ represents substituted or unsubstituted aryl (e.g. phenyl,α-naphthyl, β-naphthyl, tolyl, xylyl, biphenyl, ethylphenyl,diethylphenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl,ethoxyphenyl, diethoxyphenyl, amyloxyphenyl, hydroxyphenyl,chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl,dibromophenyl, tribromophenyl, nitrophenyl, dimethylaminophenyl,diethylaminophenyl, dibenzylaminophenyl, or diphenylaminophenyl), orsubstituted or unsubstituted heterocyclic residue (e.g. 3-carbazolyl,9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl,7-nitro-9-ethyl-3-carbazolyl, 2-pyridyl, 4-pyridyl, 2-quinolyl,4-quinolyl, 3-indolyl, 2-phenyl-3-indolyl, or1-methyl-2-phenyl-3-indolyl).

R₃₄ and R₃₅ each represent hydrogen or alkyl (e.g. methyl, ethyl,propyl, butyl, amyl, hexyl, octyl, or nonyl). The letter d is 1 or 2 ande is 0, 1, or 2. When e is 2, the two R₃₄ are the same or different andthe two R₃₅ are the same or different. X.sup.⊖ represents an anion (e.g.perchlorate, fluoroborate, iodide, chloride, bromide, sulfate,periodate, or p-toluenesulfonate anion).

Typical pyrylium dyes represented by Formula (3) are as follows:

    __________________________________________________________________________    Compound No.                                                                          Chemical Formula                                                      __________________________________________________________________________    II-(1)                                                                                 ##STR46##                                                                    ClO.sub.4.sup.⊖                                               II-(2)                                                                                 ##STR47##                                                                    ClO.sub.4.sup.⊖                                               II-(3)                                                                                 ##STR48##                                                                    ClO.sub.4.sup.⊖                                               II-(4)                                                                                 ##STR49##                                                                    ClO.sub.4.sup.⊖                                               II-(5)                                                                                 ##STR50##                                                                    ClO.sub.4.sup.⊖                                               II-(6)                                                                                 ##STR51##                                                                    ClO.sub.4.sup.⊖                                               II-(7)                                                                                 ##STR52##                                                                    ClO.sub.4.sup.⊖                                               II-(8)                                                                                 ##STR53##                                                                    ClO.sub.4.sup.⊖                                               II-(9)                                                                                 ##STR54##                                                                    ClO.sub.4.sup.⊖                                               II-(10)                                                                                ##STR55##                                                                    ClO.sub.4.sup.⊖                                               II-(11)                                                                                ##STR56##                                                                    ClO.sub.4.sup.⊖                                               II-(12)                                                                                ##STR57##                                                                    ClO.sub.4.sup.⊖                                               II-(13)                                                                                ##STR58##                                                                    ClO.sub.4.sup.⊖                                               II-(14)                                                                                ##STR59##                                                                    ClO.sub.4.sup.⊖                                               II-(15)                                                                                ##STR60##                                                                    ClO.sub.4.sup.⊖                                               II-(16)                                                                                ##STR61##                                                                    ClO.sub.4.sup.⊖                                               II-(17)                                                                                ##STR62##                                                                    ClO.sub.4.sup.⊖                                               II-(18)                                                                                ##STR63##                                                                    ClO.sub.4.sup.⊖                                               II-(19)                                                                                ##STR64##                                                                    ClO.sub.4.sup.⊖                                               II-(20)                                                                                ##STR65##                                                                    ClO.sub.4.sup.⊖                                               II-(21)                                                                                ##STR66##                                                                    ClO.sub.4.sup.⊖                                               II-(22)                                                                                ##STR67##                                                                    ClO.sub.4.sup.⊖                                               II-(23)                                                                                ##STR68##                                                                    ClO.sub.4.sup.⊖                                               II-(24)                                                                                ##STR69##                                                                    Br.sup. ⊖                                                     II-(25)                                                                                ##STR70##                                                                    ClO.sub.4.sup.⊖                                               II-(26)                                                                                ##STR71##                                                                    ClO.sub.4.sup.⊖                                               II-(27)                                                                                ##STR72##                                                                    ClO.sub.4.sup.⊖                                               II-(28)                                                                                ##STR73##                                                                    ClO.sub.4.sup.⊖                                               II-(29)                                                                                ##STR74##                                                                    ClO.sub.4.sup.⊖                                               II-(30)                                                                                ##STR75##                                                                    ClO.sub.4.sup.⊖                                               II-(31)                                                                                ##STR76##                                                                    ClO.sub.4.sup.⊖                                               II-(32)                                                                                ##STR77##                                                                    ClO.sub.4.sup.⊖                                               II-(33)                                                                                ##STR78##                                                                    ClO.sub.4.sup.⊖                                               II-(34)                                                                                ##STR79##                                                                    ClO.sub.4.sup.⊖                                               II-(35)                                                                                ##STR80##                                                                    ClO.sub.4.sup.⊖                                               II-(36)                                                                                ##STR81##                                                                    ClO.sub.4.sup.⊖                                               II-(37)                                                                                ##STR82##                                                                    ClO.sub.4.sup.⊖                                               II-(38)                                                                                ##STR83##                                                                    ClO.sub.4.sup.⊖                                               II-(39)                                                                                ##STR84##                                                                    ClO.sub.4.sup.⊖                                               II-(40)                                                                                ##STR85##                                                                    ClO.sub.4.sup.⊖                                               II-(41)                                                                                ##STR86##                                                                    ClO.sub.4.sup.⊖                                               II-(42)                                                                                ##STR87##                                                                    ClO.sub.4.sup.⊖                                               II-(43)                                                                                ##STR88##                                                                    ClO.sub.4.sup.⊖                                               II-(44)                                                                                ##STR89##                                                                    ClO.sub.4.sup.⊖                                               II-(45)                                                                                ##STR90##                                                                    ClO.sub.4.sup.⊖                                               II-(46)                                                                                ##STR91##                                                                    ClO.sub.4.sup.⊖                                               II-(47)                                                                                ##STR92##                                                                    ClO.sub.4.sup.⊖                                               II-(48)                                                                                ##STR93##                                                                    ClO.sub.4.sup.⊖                                               II-(49)                                                                                ##STR94##                                                                    ClO.sub.4.sup.⊖                                               II-(50)                                                                                ##STR95##                                                                    ClO.sub.4.sup.⊖                                               II-(51)                                                                                ##STR96##                                                                    ClO.sub.4.sup.⊖                                               II-(52)                                                                                ##STR97##                                                                    ClO.sub.4.sup.⊖                                               II-(53)                                                                                ##STR98##                                                                    ClO.sub.4.sup.⊖                                               II-(54)                                                                                ##STR99##                                                                    ClO.sub.4.sup.⊖                                               II-(55)                                                                                ##STR100##                                                                   ClO.sub.4.sup.⊖                                               __________________________________________________________________________

Pyrylium dyes of this invention can be obtained by reacting, forexample, a salt of 2,6- diphenyl-4-methyl-thiapyrylium with4-diethylaminobenzaldehyde. This reaction can be conducted in thepresence of an amine or in a carboxylic acid anhydride. i) Reaction inthe presence of amine: Though various solvents are acceptable for thisreaction, suitable ones are alcohols such as ethanol, nitriles such asacetonitrile, ketones such as methyl ethyl ketone, nitro compounds suchas nitrobenzene, halogenated hydrocarbons such as tetrachloroethane,etc., preferred ones of which are alcohols such as ethanol.

Suitable amines in this case are primary, secondary and tertiary alkylamines having 1-25 carbon atoms, such as piperidine, triethylamine, andhexylamine; aromatic amines having 6-25 carbon atoms, such as anilineand dimethylaniline; and nitrogen-containing unsaturated heterocycliccompounds such as pyridine and quinoline.

The amount of amine used ranges from 0.1 to 10 moles, preferably from0.5 to 2 moles, per mole of the thiapyrylium salt. Sometimes, the amineis used in large excess also as a solvent. The reaction is carried outfor 30 minutes-10 hours, preferably for 1-3 hours, at temperatures ofabout 50° C. to about the reflux temperature of the amine or thesolvent, preferably at temperatures around the reflux temperature. Theamount of the solvent ranges from 1 to 100 ml, preferably from 3 to 10ml, for 1 g of the salt of 2,6-diphenyl-4-methylthiapyrylium. ii)Reaction in carboxylic acid anhydride: The amount of carboxylic acidanhydride, for example in the case of acetic anhydride, ranges from 1 to20 ml, preferably from 2 to 10 ml, for 1 g of the salt of2,6-diphenyl-4-methylthiapyrylium. The reaction is carried out for 1minute to 1 hour, preferably for 3 to 20 minutes, at temperatures ofabout 80° C. to about the reflux temperature of the acid anhydride (140°C. in the case of acetic anhydride), preferably at about 100° C.

Preparation examples are given below referring to typical pyrylium saltsused in this invention.

PREPARATION EXAMPLE 2 Synthesis of a pyrylium: the above-cited compoundNo. II-(45)

A mixture of 5.0 g of 2,6-diphenyl-4-methylpyrylium perchlorate and 3.7g of 4-dimethylaminobenzaldehyde was heated in 140 ml of aceticanhydride at 95° C. for 20 minutes. The mixture was left to cool, andthe precipitate obtained by filtration was recrystallized from a 1:1acetic acid-acetic anhydride mixture, thus giving 1.8 g of a dye; m. p.271°-272° C.

Analysis for C₂₇ H₂ O₅ NCl: Calcd (%); C 67.85, H 5.07, N 2.93 Found(%); C 68.01, H 5.11, N 2.88.

PREPARATION EXAMPLE 3 Synthesis of a thiapyrylium: the above-citedcompound No. II-(29)

In 150 ml of acetone was dispersed 1.4 g of the pyrylium [compound No.II-(45)] obtained in Preparation Example 2. A solution of 1 g of sodiumsulfide in 10 ml of water was added thereto. The mixture was stirred for2 minutes and further for 1 hour with 15 ml of 20% aqueous perchloricacid and 150 ml of water. After standing, the resulting precipitate wasfiltered off and recrystallized from a 1:1 acetic acid-acetic anhydridemixture, thus giving 1.1 g of a dye; m. p. 277°-281.5° C.

Analysis for C₂₇ H₂₄ O₄ NClS: Calcd (%); C 65.64, H 4.91, S 6.49, Found(%): C 65.88, H 4.84, S 6.56.

In Formula (4), Z₄₃ and Z₄₄ each represent sulfur, oxygen, or selenium;Z₄₁ represents a hydrocarbon residue necessary to complete a pyrylium,thiapyrylium, selenapyrylium, benzopyrylium, benzothiapyrylium,benzoselenapyrylium, naphthopyrylium, naphthothiapyrylium, ornaphthoselenapyrylium ring which may be substituted or not; and Z₄₂represents a hydrocarbon residue necessary to complete a pyrane,thiapyrane, selenapyrane, benzopyrane, benzothiopyrane,benzoselenapyrane, naphthopyrane, naphthothiapyrane, ornaphthoselenapyrane ring which may be substituted or not. Suitablesubstituents on these rings include halogens (e.g. chlorine, bromine,and fluorine), alkyls (e.g. methyl, ethyl, propyl, isopropyl, butyl,t-butyl, amyl, isoamyl, hexyl, octyl, nonyl, and dodecyl), alkoxyls(e.g. methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy, and octoxy),aryls (e.g. phenyl, α-naphthyl, and β-naphthyl), and substituted aryls(e.g. tolyl, xylyl, biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl,amyloxyphenyl, dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl,chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl,diethylaminophenyl, dimethylaminophenyl, and dibenzylaminophenyl).

R₄₁, R₄₂, R₄₃, and R₄₄ each represent hydrogen, alkyl particularly a C₁-C₁₅ alkyl (e.g. methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl,isoamyl, hexyl, octyl, nonyl, or dodecyl), aryl (e.g. phenyl,α-naphthyl, or β-naphthyl), or substituted aryl (e.g. tolyl, xylyl,biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl,dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl, chlorophenyl,dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl,diethylaminophenyl, dimethylaminophenyl, or dibenzylaminophenyl).

R₄₅, R₄₆, and R₄₇ each represent hydrogen, halogen (e.g. chlorine,bromine, or fluorine), alkyl or substituted alkyl (e.g. methyl, ethyl,propyl, butyl, amyl, hydroxyethyl, methoxyethyl, or carboxypropyl), arylor substituted aryl (e.g. phenyl, tolyl, xylyl, hydroxyphenyl,carboxyphenyl, α-naphthyl, or β-naphthyl), or aralkyl or substitutedaralkyl (e.g. benzyl, phenethyl, 3-phenylpropyl, methoxybenzyl, ormethylbenzyl).

X.sup.⊖ represents an anion (e.g. perchlorate, fluoroborate, iodide,chloride, bromide, sulfate, periodate, or p-toluene-sulfonate anion).

The letters f and h are each 1 or 2 and g is 0, 1, or 2. When g is 2,the two R₄₅ may be the same or different and the two R₄₆ may be the sameor different.

Typical pyrylium dyes represented by Formula (4) are as follows:

    __________________________________________________________________________    Compound No.                                                                          Chemical Formula                                                      __________________________________________________________________________    III-(1)                                                                                ##STR101##                                                                   ClO.sub.4.sup.⊖                                               III-(2)                                                                                ##STR102##                                                                   ClO.sub.4.sup.⊖                                               III-(3)                                                                                ##STR103##                                                                   ClO.sub.4.sup.⊖                                               III-(4)                                                                                ##STR104##                                                                   ClO.sub.4.sup.⊖                                               III-(5)                                                                                ##STR105##                                                                   ClO.sub.4.sup.⊖                                               III-(6)                                                                                ##STR106##                                                                   ClO.sub.4.sup.⊖                                               III-(7)                                                                                ##STR107##                                                                   ClO.sub.4.sup.⊖                                               III-(8)                                                                                ##STR108##                                                                   ClO.sub.4.sup.⊖                                               III-(9)                                                                                ##STR109##                                                                   ClO.sub.4.sup.⊖                                               III-(10)                                                                               ##STR110##                                                                   ClO.sub.4.sup.⊖                                               III-(11)                                                                               ##STR111##                                                                   ClO.sub.4.sup.⊖                                               III-(12)                                                                               ##STR112##                                                                   ClO.sub.4.sup.⊖                                               III-(13)                                                                               ##STR113##                                                                   ClO.sub.4.sup.⊖                                               III-(14)                                                                               ##STR114##                                                                   ClO.sub.4.sup.⊖                                               III-(15)                                                                               ##STR115##                                                                   ClO.sub.4.sup.⊖                                               III-(16)                                                                               ##STR116##                                                                   ClO.sub.4.sup.⊖                                               III-(17)                                                                               ##STR117##                                                                   ClO.sub.4.sup.⊖                                               III-(18)                                                                               ##STR118##                                                                   ClO.sub.4.sup.⊖                                               III-(19)                                                                               ##STR119##                                                                   ClO.sub.4.sup.⊖                                               III-(20)                                                                               ##STR120##                                                                   ClO.sub.4.sup.⊖                                               III-(21)                                                                               ##STR121##                                                                   ClO.sub.4.sup.⊖                                               III-(22)                                                                               ##STR122##                                                                   ClO.sub.4.sup.⊖                                               III-(23)                                                                               ##STR123##                                                                   ClO.sub.4.sup.⊖                                               III-(24)                                                                               ##STR124##                                                                   ClO.sub.4.sup.⊖                                               __________________________________________________________________________

These compounds can be prepared according to a method described in, forexample, U.S. Pat. No. 4,315,983.

In Formula (5), which represents polymethine dyes, A, B, D, and E eachrepresent aryl or substituted aryl (e.g. phenyl, tolyl, xylyl,ethylphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl,dibromophenyl, nitrophenyl, methoxyphenyl, ethoxyphenyl,dimethylaminophenyl, diethylaminophenyl, dipropylaminophenyl,dibenzylaminophenyl, or diphenylaminophenyl); R₅₁, R₅₂, R₅₃, R₅₄, andR₅₅ each represent hydrogen, halogen (e.g. chlorine or bromine), oralkyl (e.g. methyl, ethyl, propyl, butyl, or amyl); Y represents adivalent residue (e.g. ethylene, propylene, or o-phenylene) necessary tocomplete a 5- or 6-membered ring; and X.sup.⊖ represents an anion (e.g.perchlorate, fluoroborate, iodide, chloride, bromide, orp-toluenesulfonate anion).

Typical polymethine dyes represented by Formula (5) are shown below.

    __________________________________________________________________________    Compound No.                                                                          Chemical Formula                                                      __________________________________________________________________________    IV-(1)                                                                                 ##STR125##                                                           IV-(2)                                                                                 ##STR126##                                                           IV-(3)                                                                                 ##STR127##                                                           IV-(4)                                                                                 ##STR128##                                                           IV-(5)                                                                                 ##STR129##                                                           IV-(6)                                                                                 ##STR130##                                                           IV-(7)                                                                                 ##STR131##                                                           IV-(8)                                                                                 ##STR132##                                                           IV-(9)                                                                                 ##STR133##                                                           IV-(10)                                                                                ##STR134##                                                           IV-(11)                                                                                ##STR135##                                                           IV-(12)                                                                                ##STR136##                                                           IV-(13)                                                                                ##STR137##                                                           IV-(14)                                                                                ##STR138##                                                           IV-(15)                                                                                ##STR139##                                                           IV-(16)                                                                                ##STR140##                                                           IV-(17)                                                                                ##STR141##                                                           IV-(18)                                                                                ##STR142##                                                           IV-(19)                                                                                ##STR143##                                                           IV-(20)                                                                                ##STR144##                                                           IV-(21)                                                                                ##STR145##                                                           IV-(22)                                                                                ##STR146##                                                           IV-(23)                                                                                ##STR147##                                                           IV-(24)                                                                                ##STR148##                                                           IV-(25)                                                                                ##STR149##                                                           IV-(26)                                                                                ##STR150##                                                           __________________________________________________________________________

These polymethine dyes can be prepared according to a method describedin, for example, Japanese Patent No. 8149/1981.

In Formula (6), which represents polymethine dyes, R₆₁, R₆₂, R₆₃, R₆₄,and R₆₅ each represent hydrogen, alkyl (e.g. methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-amyl, t-amyl,n-hexyl, n-octyl, or t-octyl), substituted alkyl (e.g. 2-hydroxyethyl,3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl, carboxymethyl,2-carboxyethyl, 3-carboxypropyl, 2-sulfoethyl, 3-sulfopropyl,4-sulfobutyl, 3-sulfatepropyl, 4-sulfatebutyl,N-(methylsulfonyl)carbamylmethyl, 3-(acetylsulfamyl)propyl, or4-(acetylsulfamyl)butyl), cycloalkyl (e.g. cyclohexyl), alkenyl (e.g.allyl-(CH₂ ═CH--CH₂ --), aralkyl (e.g. benzyl, phenethyl, α-naphthyl, orβ-naphthyl), substituted aralkyl (e.g. carboxybenzyl, sulfobenzyl, orhydroxybenzyl), aryl or substituted aryl (e.g. phenyl, naphthyl, tolyl,xylyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl,dimethylaminophenyl, diethylaminophenyl, dipropylaminophenyl,dibenzylaminophenyl, or diphenylaminophenyl), substituted orunsubstituted heterocyclic residue (e.g. pyridyl, quinolyl, lepidyl,methylpyridyl, furyl, thienyl, indolyl, pyrrolyl, carbazolyl, orN-ethylcarbazolyl), or styryl or substituted styryl (e.g. methoxystyryl,dimethoxystyryl, trimethoxystyryl, ethoxystyryl, dimethylaminostyryl,diethylaminostyryl, dipropylaminostyryl, dibenzylaminostyryl,diphenylaminostyryl, 2,2-diphenylvinyl, 2-phenyl-2-methylvinyl,2-dimethylaminophenyl-2-phenylvinyl, 2-diethylaminophenyl-2-phenylvinyl, 2-dibenzylaminophenyl-2-phenylvinyl,2,2-di(diethylaminophenyl)vinyl, 2,2-di(methoxyphenyl)vinyl,2,2-di(ethoxyphenyl)vinyl, 2-dimethylaminophenyl-2-methylvinyl, or2-diethylaminophenyl-2-ethylvinyl); i is 0 or 1, j is 0, 1 or 2; andX.sup.⊖ represents an anion (e.g. chloride, bromide, iodide,perchlorate, benzenesulfonate, p-toluenesulfonate, methylsulfate,ethylsulfate, or propylsulfate anion).

Typical examples of the polymethine compounds represented by Formula (6)are given below.

    __________________________________________________________________________    Compound No.                                                                          Chemical Formula                                                      __________________________________________________________________________    V-(1)                                                                                  ##STR151##                                                           V-(2)                                                                                  ##STR152##                                                           V-(3)                                                                                  ##STR153##                                                           V-(4)                                                                                  ##STR154##                                                           V-(5)                                                                                  ##STR155##                                                           V-(6)                                                                                  ##STR156##                                                           V-(7)                                                                                  ##STR157##                                                           V-(8)                                                                                  ##STR158##                                                           V-(9)                                                                                  ##STR159##                                                           V-(10)                                                                                 ##STR160##                                                           V-(11)                                                                                 ##STR161##                                                           V-(12)                                                                                 ##STR162##                                                           V-(13)                                                                                 ##STR163##                                                           V-(14)                                                                                 ##STR164##                                                           V-(15)                                                                                 ##STR165##                                                           V-(16)                                                                                 ##STR166##                                                           V-(17)                                                                                 ##STR167##                                                           V-(18)                                                                                 ##STR168##                                                           V-(19)                                                                                 ##STR169##                                                           V-(20)                                                                                 ##STR170##                                                           __________________________________________________________________________

These polymethine compounds can be readily prepared according tosynthetic methods disclosed by Bernard S. Wildi et al. in J. Am. Chem.Soc., 80, 3772-3777 (1958), H. Schmidt et al. in Ann., 623, 204-216, andR. Wizinger et al. in Helv. Chim. Acta., 24, 369, etc.

In formula (7), which represents cyanine dyes, Z₇₁ and Z₇₂ eachrepresent a nonmetal atomic group necessary to complete anitrogen-containing heterocyclic ring substituted or unsubstituted, suchas a thiazole family ring (e.g. thiazole, 4-methylthiazole,4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole,4,5-dimethylthiazole, 4,5-diphenylthiazole, or 4-(2-thienyl) thiazole),benzothiazole family ring (e.g. benzothiazole, 5-chlorobenzothiazole,5-methylbenzothiazole, 6-methylbenzothiazole, 5,6-dimethylbenzothiazole,5-bromobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole,6-methoxybenzothiazole, 5,6-dimethoxybenzothiazole,5,6-hydroxymethylbenzothiazole, 5-hydroxybenzothiazole,6-hydroxybenzothiazole, or 4,5,6,7-tetrahydrobenzothiazole),naphthothiazole family ring (e.g. naphtho (2,1-d) thiazole, naphtho(1,2-d) thiazole, 5-methoxynaphtho (1,2-d) thiazole, 5-ethoxynaphtho(1,2-d) thiazole, 8-methoxynaphtho (2,2-d) thiazole, or 7-methoxynaphtho(2,2-d) thiazole), thianaphthene family ring (e.g.7-methoxythianaphthene (7,6-d) thiazole), oxazole family ring (e.g.4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole,4-ethyloxazole, 4,5-dimethyloxazole, or 5-phenyloxazole), benzoxazolefamily ring (e.g. benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole,5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole,5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, or6-hydroxybenzoxazole), naphthoxazole family ring (e.g. naphtho [2,1-d]oxazole or naphtho [1,2-d] oxazole), selenazole family ring (e.g.4-methylselenazole or 4-phenylselenazole), benzoselenazole family ring(e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methylbenzoselenazole,5,6-dimethylbenzoselenazole, 5-methoxybenzoselenazole,5-methyl-6-methoxybenzoselenazole,5,6-dihydroxymethylbenzoselenazole,5-hydroxybenzoselenazole, or 4,5,6,7-tetrahydroselenazole),naphthoselenazole family ring (e.g. naphtho [2,1-d] selenazole ornaphtho [1,2-d] selenazole), thiazoline family ring (e.g. thiazoline,4-methylthiazoline, 4-hydroxymethyl-4-methylthiazoline, or4,4-dihydroxymethylthiazoline), oxazoline family ring (e.g. oxazoline),selenazoline family ring (e.g. selenazoline), 2-quinolyl family ring(e.g. quinoline, 6-methylquinoline, 6-chloroquinoline,6-methoxyquinoline, 6-ethoxyquinoline, or 6-hydroxyquinoline),4-quinolyl family ring (e.g. quinoline, 6-methoxyquinoline,7-methylquinoline, or 8-methylquinoline), 1-isoquinolyl family ring(e.g. isoquinoline or 3,4-dihydroxyisoquinoline), 3-isoquinolyl familyring (e.g. isoquinoline), 3,3-dialkylindolenine family ring (e.g.3,3-dimethylindolenine, 3,3-dimethyl-5-chloroindolenine,3,3,5-trimethylindolenine, or 3,3,7-trimethylindolenine), pyridinefamily ring (e.g. pyridine or 5-methylpyridine), or benzimidazole familyring (e.g. 1-ethyl-5,6-dichlorobenzimidazole,1-hydroxyethyl-5,6-dichlorobenzimidazole,1-ethyl-5-chlorobenzoimidazole, 1-ethyl-5,6-dibromobenzimidazole,1-ethyl-5-phenylbenzimidazole, 1-ethyl-5-fluorobenzimidazole,1-ethyl-5-cyanobenzimidazole, 1-(β-acetoxyethyl)-5-cyanobenzimidazole,1-ethyl-5-chloro-6 - cyanobenzimidazole,1-ethyl-5-fluoro-6-cyanobenzimidazole, 1-ethyl-5-acetylbenzimidazole,1-ethyl-5-carboxybenzimidazole, 1-ethyl-5-ethoxycarbonylbenzimidazole,1-ethyl-5-sulfamylbenzimidazole, 1-ethyl-5-N-ethylsulfamylbenzimidazole,1-ethyl-5,6-difluorobenzimidazole, 1-ethyl-5,6-dicyanobenzimidazole,1-ethyl-5-ethylsulfonylbenzimidazole,1-ethyl-5-methylsulfonylbenzimidazole,1-ethyl-5trifluoromethylbenzimidazole,1-ethyl-5-trifluoromethylsulfonylbenzimidazole, or1-ethyl-5-trifluoromethylsulfinylbenzimidazole).

A₁ and A₂ each represent a divalent hydrocarbon residue (e.g. --CH₂--CH₂ --, --CH₂ --CH₂ --CH₂ --, ##STR171## or --CH═CH--) necessary toform a substituted or unsubstituted 5- or 6-membered ring, which iscondensed or not with a benzene ring, naphthalene ring, or the like.

R₇₁ and R₇₂ each represent hydrogen, alkyl (e.g. methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-amyl,t-amyl, n-hexyl, n-octyl, or t-octyl), substituted alkyl (e.g.2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl,carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 2-sulfoethyl,3-sulfopropyl, 4-sulfobutyl, 3-sulfatepropyl, 4-sulfatebutyl,N-(methylsulfonyl)carbomylmethyl, 3-acethylsulfamylpropyl, or4-acetylsulfamylbutyl), cycloalkyl (e.g. cyclohexyl), alkenyl (e.g.allyl (CH₂ ═CH--CH₂ --)), aralkyl (e.g. benzyl, phenethyl,α-naphthylmethyl, or β-naphthylmethyl), or substituted aralkyl (e.g.carboxybenzyl, sulfobenzyl, or hydroxybenzyl).

R₇₃ and R₇₄ each represent hydrogen or halogen (e.g. chlorine, bromine,or iodine).

X.sup.⊖ an anion (e.g. chloride, bromide, iodide, perchlorate,benzenesulfonate, p-toluenesulfonate, methylsufate, ethylsulfate, orpropylsulfate anion). However, X.sup.⊖ is not contained in Formula (7)when R₇₁ or R₇₂ itself has an anion (e.g. --SO₃.sup.⊖, OSO₃.sup.⊖,--COO.sup.⊖, SO₂.sup.⊖ NH--, --SO₂ --N.sup.⊖ --CO--, --SO₂ --N.sup.⊖--SO₂ --. The letters m and k are each 0 or 1, and l is 1 or 2.

Typical examples of the cyanine compounds represent by Formula (7) areshown below. ##STR172##

These compounds can be prepared according to a method described in, forexample, U S. Pat. No. 2,734,900.

In Formula (8), which represents cyanine dyes, Z₈₁ and Z₈₂ eachrepresent a nonmetal atomic group necessary to complete a substituted orunsubstituted nitrogen-containing heterocyclic ring such as a thiazolefamily ring (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole,5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole,4,5-diphenylthiazole, or 4-(2-thienyl)thiazole), benzothiazole familyring (e.g. benzothiazole, 5-chlorobenzothiazole, -methylbenzothiazole,6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-bromobenzothiazole,5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole,5,6-dimethoxybenzothiazole, 5,6-dihydromethylbenzothiazole,5-hydroxybenzothiazole, 6-hydroxybenzothiazole, or4,5,6,7-tetrahydrobenzothiazole), naphthothiazole family ring (e.g.naphtho(2,1d)thiazole, naphtho(1,2-d)thiazole,5-methoxynaphtho(1,2-d)thiazole, 5-ethoxynaphtho-(1,2-d)thiazole,,8-methoxynaphtho(2,1-d)thiazole, or 7-methoxynaphtho(2,1-d)thiazole),thionaphthene(7,6-d)thiazole family ring (e.g.7-methoxythionaphthene(7,6-d)thiazole), oxazole family ring (e.g.4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole,4-ethyloxazole, 4,5-dimethyloxazole, or 5-phenyloxazole), benzoxazolefamily ring (e.g. benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole,5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole,5-methoxybenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, or6-hydroxybenzoxazole), naphthoxazole family ring (e.g.naphto[2,1-d]oxazole or naphtho[1,2-d]oxazole), selenazole family ring(e.g. 4-methylselenazole or 4-phenylselenazole), benzoselenazole familyring (e.g. benzoselenazole, 5-chlorobenzoselenazole,5-methylbenzoselenazole, 5,6-dimethylbenzoselenazole,5-methoxybenzoselenazole, 5-methyl-6-methoxybenzoselenazole,5,6-dihydroxymethylbenzoselenazole, 5-hydroxybenzoselenazole, or4,5,6,7-tetrahydrobenzoselenazole), naphthoselenazole family ring (e.g.naphtho(2,1-d)selenazole or naphtho(1,2-d)selenazole), thiazoline familyring (e.g. thiazoline, 4-methylthiazoline,4-hydroxymethyl-4-methylthiazoline, or 4,4-dihydroxymethylthiazoline),oxazoline family ring (e.g. oxazoline), selenazoline family ring (e.g.selenazoline), 2-quinolyl family ring (e.g. quinoline,6-methylquinoline, 6-chloroquinoline, 6-methoxyquinoline,6-ethoxyquinoline, or 6-hydroxyquinoline), 4-quinolyl family ring (e.g.quinoline, 6-methoxyquinoline, 7-methylquinoline, or 8-methylquinoline),1-isoquinolyl family ring (e.g. isoquinoline or3,4-dihydroxyisoquinoline), 3-isoquinolyl family ring (e.g.isoquinoline), 3,3-dialkylindolenine family ring (e.g.3,3-dimethylindolenine, 3,3-dimethyl-5-chloroindolenine,3,3,5-trimethylindolenine, or 3,3,7-trimethylindolenine), pyridinefamily ring (e.g. pyridine or 5-methylpyridine), or benzimidazole familyring (e.g. 1-ethyl-5,6-dichlorobenzimidazole,1-hydroxyethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole,1-ethyl-5,6-dibromobenzimidazole, 1-ethyl-5-phenylbenzimidazole,1-ethyl-5-fluorobenzimidazole, 1-ethyl-5-cyanobenzimidazole,1-(β-acetoxyethyl)-5-cyanobenzimidazole,1-ethyl-5-chloro-6-cyanobenzimidazole,1-ethyl-5-fluoro-6-cyanobenzimidazole, 1-ethyl-5-acetylbenzimidazole,1-ethyl-5-carboxybenzimidazole, 1-ethyl-5-ethoxycabonylbenzimidazole,1-ethyl-5-sulfamylbenzimidazole, 1-ethyl-5-N-ethylsulfamylbenzimidazole,1-ethyl-5,6-difluorobenzimidazole, 1-ethyl-5,6-dicyanobenzimidazole,1-ethyl-5-ethylsulfonylbenzimidazole,1-ethyl-5-methylsulfonylbenzimidazole,1-ethyl-5-trifluoromethylbenzimidazole,1-ethyl-5-trifluoromethylsulfonylbenzimidazole, or1-ethyl-5-trifluoromethylsulfinylbenzimidazole).

Z₈₃ represents a divalent hydrocarbon residue (e.g. --CH₂ --CH₂ --,--CH₂ --CH₂ --CH₂ --, --CH═CH--, or --CH═CH--CH₂ --) necessary tocomplete a 5- or 6-membered ring, which is condensed or not with abenzene ring, naphthalene ring, or the like.

R₈₁ and R₈₂ each represent hydrogen, alkyl (e.g. methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-amyl,t-amyl, n-hexyl, n-octyl, or t-octyl), substituted alkyl (e.g.2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-acetoxyethyl,carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 2-sulfoethyl,3-sulfopropyl, 4-sulfobutyl, 3-sulfatepropyl, 4-sulfatebutyl,N-(methylsulfonyl)carbamylmethyl, 3-(acetylsulfamyl)propyl, or4-(acetylsulfamyl)butyl), cycloalkyl (e.g. cyclohexyl), alkenyl (e.g.allyl (CH₂ ═CH--CH₂ --)), aralkyl (e.g. benzyl, phenethyl,α-naphthylmethyl, or β-naphthylmethyl), or substituted aralkyl (e.g.carboxybenzyl, sulfobenzyl, or hydroxybenzyl).

Q represents oxygen, sulfur, imino, or substituted imino (e.g.methylimino, ethylimino, propylimino, butylimino, or benzylimino), ororganic divalent residue, ##STR173## wherein R₈₃, R₈₄ and R₈₅ eachrepresent hydrogen or alkyl (similar as cited above referring to R₈₁ andR₈₂).

The letter s, t, and r are each 0 or 1 and p and q are each 0, 1, or 2.

Typical examples of the cyanine dyes represented by Formula (8) aregiven below. ##STR174##

These cyanine compounds can be readily obtained by condensation a cyclicketone such as indan-2-one, cyclohexanone, cyclopentanone,cyclohexene-one, cyclopentadiene-one, or1,2,3,4-tetrahydronaphtalene-2-one with dicyanomethane, barbituric acidor its derivative, or rhodanine or its derivative, and reacting thecondensation product with a benzothiazolium salt, benzoxazolium salt,quinolium salt, or naphthothiazolium salt, these salts being generallyin use in the field of cyanine chemistry.

In Formula (9), which represents pyrylium dyes, Z₉₃ and Z₉₄ eachrepresent sulfur, oxygen, or selenium; Z₉₁ represents an atomic groupnecessary to complete a pyrylium, thiapyrylium, selenapyrylium,benzopyrylium, benzothiapyrylium, benzoselenapyrylium, naphthopyrylium,naphthothiapyrylium, or naphthoselenapyrylium ring which may besubstituted or not; and Z₉₂ represents an atomic group necessary to apyrane, thiapyrane, selenapyrane, benzopyrane, benzothiapyrane,benzoselenapyrane, naphthopyrane, naphthothiapyrane, ornaphthoselenapyrane ring which may be substituted or not. Suitablesubstituents on these rings include alkyls (e.g. methyl, ethyl,n-propyl, isopropyl, n-butyl, t-butyl, n-amyl, t-amyl, n-hexyl, n-octyl,t-octyl, and 2-ethylhexyl), alkoxyls (e.g. methoxy, ethoxy, propoxy, andbutoxy), aryls and substituted aryls (e.g. phenyl, tolyl, xylyl,biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, diethoxyphenyl,hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl,nitrophenyl, diethylaminophenyl, dimethylaminophenyl, anddibenzylaminophenyl), styryl substituted styryls (e.g. methoxystyryl,dimethoxystyryl, ethoxystyryl, diethoxystyryl, and dimethylaminostyryl),4-phenyl-1,3-butadienyl, substituted 4-phenyl-1,3-butadienyls (e.g.4-(p-dimethylaminophenyl)-1,3-butadienyl and4-(p-diethylaminophenyl)-1,3-butadienyl), and heterocyclic residues(e.g. 3-carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl, and9-carbazolyl).

A₃.sup.⊖ represents ##STR175##

R₉₁, R₉₂, R₉₃ and R₉₄ each represent hydrogen, alkyl, particularly C₁-C₁₅ alkyl (e.g. methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl,isoamyl, hexyl, octyl, nonyl, or dodecyl), alkoxyl (e.g. methoxy,ethoxy, propoxy, butoxy, amyloxy, hexoxy, or octoxy), aryl (e.g. phenyl,α-naphthyl, or β-naphthyl), substituted aryl (e.g. tolyl, xylyl,biphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, amyloxyphenyl,dimethoxyphenyl, diethoxyphenyl, hydroxyphenyl, chlorophenyl,dichlorophenyl, bromophenyl, dibromophenyl, nitrophenyl,diethylaminophenyl, dimethylaminophenyl, or dibenzylaminophenyl),styryl, substituted styryl (e.g. methoxystyryl, dimethoxystyryl,ethoxystyryl, diethoxystyryl, dimethylaminostyryl, ordiethylaminostyryl), 4-phenyl-1,3-butadienyl, substituted4-phenyl-1,3-butadienyl (e.g. 4-(p-dimethylaminophenyl)-1,3-butadienylor 4-(p-diethylaminophenyl)-1,3-butadienyl), or substituted orunsubstituted heterocyclic residue (e.g. 3-carbazolyl,9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl, or 9-carbazolyl), where R₉₁coupled with R₉₂ and R₉₃ coupled with R₉₄ can form each a substituted orunsubstituted benzene ring. The letters v and w are each 1 or 2.

Typical examples of the pyrylium dyes represented by Formula (9) are asfollows: ##STR176##

These compounds can be readily obtained, for instance, by reacting apyrylium salt represented by the formula ##STR177## (Z₉₃ is as definedabove and Z.sub.⊖ represents an anion such as a perchlorate,fluoroborate, sulfoacetate, iodide, or bromide anion) with3,4-dihydroxy-3-cyclobutene-1,2-dione, croconic acid, or its derivative(e.g. mono- or di-alkyl croconate) in a solvent.

2-Methyl-4,6-diphenylpyrylium salt, represented by the above formula,can be prepared, for instance, according to the method of Schneider etal. reported in Ber., 54, 2289 (1921) and2-methyl-4,6-diphenylthiopyrylium salt according to the method ofWizinger et al. reported in Helv. Chim. Acta., 39, 221 (1956). Besidesthese pyrylium salts, it is possible to use, as a starting material ofthe preparation, known pyrylium salts having an active methyl group,such as 2,6-di-t-butyl-4-methylthiapyrylium salt, which has beendisclosed in U.S. Pat. No. 4,315,983.

While a wide variety of organic solvents can be used for this reaction,preferred ones are alcohols such as ethanol, butanol, and benzylalcohol; nitriles such as acetonitrile and propionitrile; carboxylicacids such as acetic acid, and acid anhydrides such as acetic anhydride.An aromatic hydrocarbon such as benzene may also be used in mixture withbutanol, benzyl alcohol, or the like.

Amounts of pyrylium salt used are 1.0-5.0, preferably 1.5-3.0, molesequivalent per mole of 3,4-dihydroxy-3-cyclobutene-1,2-dione orcrocontic acid. The reaction solvent is used in amounts of 0.5-100 ml,preferably 2-10 ml, for 1 g of the whole raw material.

The reaction is carried out at temperatures of 25°-100° C., preferably60°-140° C., for 5 minutes-30 hours, preferably 20 minutes-5 hours.

To promote the reaction, a base can be added, including, for example,triethylamine, pyridine, quinoline, or sodium acetate.

Synthesis of typical compounds represented by Formula (9) is illustratedreferring to Preparation Examples 4 and 5.

PREPARATION EXAMPLE 4 synthesis of compound No. VIII-(7)

A solution was prepared by heating 1.2 g (0.0105 mole) of3,4-dihydroxy-3-cyclobutene-1,2-dione and 36 ml of n-butanol up to 100°C. while stirring in a 100 ml, three-necked flask. To the solution wereadded in succession 3 ml of quinoline 7.3 g (0.0211 mole) of2-methyl-4,6-diphenylpyrylium perchlorate, and 15 ml of benzene to startthe reaction. The reaction was continued for 3.5 hours at 95°-110° C.while adding in parts 30 ml of benzene and 20 ml of butanol and removingwater by azeotropic distillation. The reaction mixture was cooled andfiltered with suction. The filter cake was washed with 30 ml of butanolto give a crude dye. It was rinsed five times with 200 ml each ofboiling methanol and then twice with 100 ml each of boilingtetrahydrofuran, giving 1.9 g of compound No. VIII-(7); yield 31.7%,m.p. 255°-258° C.

Analysis for C₄₀ H₂₆ O₄ : Calcd. (%): C 84.18, H 4.60. Found (%): C84.02, H 4.76.

Visible-to-infrared ray absorption spectrum in dimethylformamide:

λmax 910 nm, 815 nm.

ε 6.6×10⁴, 6.2×10⁴.

PREPARATION EXAMPLE 5 Synthesis of compound No. VIII-(5)

A solution was prepared by heating 1.0 g (0.0088 mole) of3,4-dihydroxy-3-cyclobutene-1,2-dione and 50 ml of n-butanol up to 100°C. while stirring in a 100 ml, three-necked flask. To the solution wereadded in succession 2.5 ml of quinoline, 6.36 g (0.0176 mole) of2-methyl-4,6-diphenylthiapyrylium perchlorate, and 10 ml of benzene tostart reaction.

The reaction was continued for 3 hours at 95°-110° C. while adding inparts 30 ml of benzene and 10 ml of n-butanol and removing water byazeotropic distillation.

The reaction mixture was allowed to stand overnight and filtered withsuction. The cake was washed with 30 ml of n-butanol to give a crudedye. It was rinsed five times with 200 ml each of boiling methanol andthen twice with 100 ml each of boiling tetrahydrofuran, giving 1.36 g ofcompound No. VIII-(5); yield 25.7%, m.p. 232.5°-235° C.

Analysis for C₄₀ H₂₆ O₂ S₂ : Calcd. (%): C 79.70, H 4.36, S 10.64. Found(%): C 79.59, H 4.45, S 10.69.

Visible-to-infrared ray absorption spectrum in dimethyl formamide:

λmax: 975 nm 885 nm.

ε: 13×10⁴, 5.29×10⁴.

The pyrylium type compounds according to the present invention can beused also in the form of cocrystalline complex with a polymer havingrepeating units of alkylidene diarylene. Such polymers can berepresented by the formula ##STR178## wherein; R₆ and R₇ each representhydrogen, alkyl (e.g. methyl, ethyl, propyl, isopropyl, butyl, t-butyl,amyl, hexyl, octyl, nonyl, or decyl), substituted alkyl (e.g.trifluoromethyl), aryl (e.g. phenyl or naphthyl), or substituted aryl(e.g. tolyl, xylyl, ethylphenyl, propylphenyl, amylphenyl, chlorophenyl,dichlorophenyl, or bromophenyl , R₆ and R₇ being allowed to formcojointly a cycloalkane such as hexyl or a polycycloalkane such asnorbornyl; R₅ and R₈ each represent hydrogen, C₁ -C₅ alkyl, or halogen(e.g. chlorine, bromine, or iodine); and R₉ represents a divalentresidue selected from the group consisting of ##STR179##

Typical examples of these polymers are as follows

    ______________________________________                                        Polymer No.                                                                              Polymer name                                                       ______________________________________                                         1.        Poly(4,4'-isopropylidenediphenylene-CO-                                       1,4-cyclohexyl-dimethyl carbonate)                                  2.        Poly(3,3'-ethylenedioxyphenylene                                              thiocarbonate)                                                      3.        Poly(4,4'-isopropylidenediphenylene                                           carbonate-CO-terephthalate)                                         4.        Poly(4,4'-isopropylidenediphenylene                                           carbonate)                                                          5.        Poly(4,4'-isopropylidenediphenylene                                           thiacarbonate)                                                      6.        Poly(2,2-butanebis(4-phenylene)carbonate)                           7.        Poly(4,4'-isopropylidenediphenylene                                           carbonate-block-ethyleneoxide)                                      8.        Poly(4,4'-isopropylidenediphenylene                                           carbonate-block-tetramethyleneoxide)                                9.        Poly(4,4'-isopropylidenebis(2-methyl-                                         phenylene)carbonate)                                               10.        Poly(4,4'-isopropylidenediphenylene-CO-                                       1,4-phenylene carbonate)                                           11.        Poly(4,4'-isopropylidenediphenylene-CO-                                       1,3-phenylene carbonate)                                           12.        Poly(4,4'-isopropylidenediphenylene-CO-                                       4,4'-diphenylene carbonate)                                        13.        Poly(4,4'-isopropylidenediphenylene-CO-                                       4,4'-oxydiphenylene carbonate)                                     14.        Poly(4,4'-isopropylidenediphenylene-CO-                                       4,4'-carboxyldiphenylene carbonate)                                15.        Poly(4,4'-isopropylidenediphenylene-CO-                                       4,4'-ethylenediphenylene carbonate)                                16.        Poly(4,4'-methylenebis(2-methylphenylene)-                                    carbonate                                                          17.        Poly(1,1-(p-bromophenylethane)bis(4-                                          phenylene)carbonate)                                               18.        Poly(4,4'-isopropylidenediphenylene-CO-                                       sulfonylbis(4-phenylene)carbonate)                                 19.        Poly(4,4'-isopropylidenebis(2-chloro-                                         phenylene)carbonate)                                               20.        Poly(hexafluoroisopropylidenebis(4-                                           phenylene)carbonate)                                               21.        Poly(4,4'-isopropylidenediphenylene                                           4,4'-isopropylidenedibenzoate)                                     22.        Poly(4,4'-isopropylidenedibenzyl 4,4'-                                        isopropylidenedibenzoate)                                          23.        Poly(2,2-(3-methylbutane)bis(4-phenylene)-                                    carbonate)                                                         24.        Poly(2,2-(3,3-dimethylbutane)bis(4-                                           phenylene)carbonate)                                               25.        Poly(1,1-(1-naphthyl)bis(4-phenylene)-                                        carbonate)                                                         26.        Poly(2,2-(4-methylpentane)bis(4-phenylene)-                                   carbonate)                                                         ______________________________________                                    

Co-crystalline complexes of the pyrylium type compound with thesepolymers can be obtained according to methods disclosed in, for example,U.S. Pat. No. 3,684,502 and austral. Patent Laid-Open No. 87757/1975,respectively. As an example, such a complex can be prepared bydissolving said pyrylium type compound and polymer in a halogenatedhydrocarbon solvent (dichloromethane) and adding a non-halogenated,nonpolar solvent (e.g. hexane, octane, decane, ligroin, or toluene) toprecipate the complex.

In Formula (10), R₂₁ and R₂₂ represent each alkyl (e.g. methyl, ethyl,propyl, or butyl) or R₂₁ and R₂₂ together with the nitrogen atom towhich they are attached form a ring residue such as morpholino,piperidino, or pyrrolidinyl; R₂₃, R₂₄, R₂₅, and R₂₆ each representhydrogen, halogen (e.g. chlorine, bromine, or iodine), alkyl (e.g.methyl, ethyl, propyl, or butyl), alkoxyl (e.g. methoxy, ethoxy,propoxy, or butoxy), or hydroxyl, where combinations of R₂₃ and R₂₄ andcombinations of R₂₅ and R₂₆ can each form a benzene ring.

Typical examples of the compounds represented by Formula (10) are asfollows:

    ______________________________________                                        Compound                                                                      No.     Chemical Formula                                                      ______________________________________                                        IX-(1)                                                                                 ##STR180##                                                           IX-(2)                                                                                 ##STR181##                                                           IX-(3)                                                                                 ##STR182##                                                           IX-(4)                                                                                 ##STR183##                                                           IX-(5)                                                                                 ##STR184##                                                           IX-(6)                                                                                 ##STR185##                                                           IX-(7)                                                                                 ##STR186##                                                           IX-(8)                                                                                 ##STR187##                                                           ______________________________________                                    

A representative example of the processes for preparing these compoundsis given below.

PREPARATION EXAMPLE 6 Synthesis of compound No. IX-(1)

A solution was prepared by mixing 10.6 g of N,N-dimethyl-m-aminophenoland 180 ml of n-buthanol in a three-necked flask. The solution, afteraddition of 5.0 g of croconic acid and 50 ml of benzene, was heated toreact at 90°-100° C. for 1 hour while distilling off water. Aftercooling, the resulting precipitate was filtered off, washed with 40 mlof n-butanol, three times with 200 ml of hot methyl Cellosolve, and with200 ml of hot tetrahydrofuran. By drying the precipitate, 6.3 g of theobjective product was obtained; yield 47%. An absorption spectrumthereof in dimethylformamide is shown in FIG. 2 (λ max=818 nm).

The optical recording medium of this invention has a structure, forexample, as shown in FIG. 4. The recording medium shown in FIG. 4 can beprepared by forming an organic thin film 2 containing a dye representedby Formulae (1)-(10), on a substrate 1. The organic thin film 2 isformable by vacuum deposition of the dye or applying a coating liquidcomprising the dye and a binder onto the substrate 1. In this case, thedye may be contained in the form of either dispersion or non-crystal, inthe binder. Suitable binders of the dye can be selected from a widevariety of resins including, for example, cellulose esters such asnitrocellulose, cellulose phosphate, cellulose sulfate, celluloseacetate, cellulose propionate, cellulose butyrate, cellulose myristate,cellulose palmitate, cellulose acetate-propionate, and celluloseacetate-butyrate; cellulose ethers such as methyl cellulose, ethylcellulose, propyl cellulose, and butyl cellulose; vinyl type resins suchas polystyrene, poly(vinyl chloride), poly(vinyl acetate), poly(vinylbutyral), poly(vinyl acetal), poly(vinyl alcohol), andpolyvinylpyrrolidone; vinyl type copolymer resins such asstyrene-butadiene copolymer, styrene-acrylonitrile copolymer,styrene-butadiene-acrylonitrile copolymer, vinyl chloride-vinylidenechloride copolymer, and vinyl chloride-vinyl acetate copolymer; acrylicresins such as poly(methyl methacrylate), poly(methyl acrylate),poly(butyl acrylate), poly(acrylic acid), poly(methacrylic acid),polyacrylamide, and polyacrylonitrile; polyesters such as poly(ethyleneterephthalate); polycarbonates and co-polyesters thereof such aspoly(4,4'-isopropylidenediphenylene CO-1,4-cyclohexylenedimethylenecarbonate), poly(ethylenedioxy3,3'-phenylene thiocarbonate),poly(4,4'-isopropylidenediphenylene carbonate),poly(4,4'-sec-butylidenediphenylene carbonate), andpoly(4,4'-isopropylidenediphenylene carbonate block-oxyethylene);polyarylates such as poly(4,4'-isopropylidenediphenylene terephthalate);polyamides; polyimides; epoxy resins; phenolic resins; and polyolefinssuch as polyethylene, polypropylene, and chlorinated polyethylene.

While the organic solvent used for the coating varies depending upon thekind of binder and upon the form of the dye dispersed or non-crystal inthe binder, generally the following solvents are suitable; alcohols suchas methanol, ethanol, and isopropanol; ketones such as acetone, methylethyl ketone, and cyclohexanone; amides such as N,N-dimethylformamideand N,N-dimethylacetamide; sulfoxides such as dimethylsulfoxide; etherssuch as tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether;esters such as methyl acetate and ethyl acetate; halogenated aliphatichydrocarbons such as chloroform, methylene chloride, dichloroethylene,carbon tetrachloride, and trichloroethylene; aromatic hydrocarbons suchas benzene, toluene, xylene, and ligroin; and halogenated aromatichydrocarbons such as monochlorobenzene and dichlorobenzene.

The coating can be accomplished by various methods including dipcoating, spray coating, spinner coating, bead coating, Meyer barcoating, blade coating, roller coating, curtain coating, and the like.

The dye content in the film 2 ranges from 1 to 90%, preferably from 20to 70%, by weight when forming the organic thin film 2 together with abinder. Dry of the film 2 is up to 10 μ, preferably up to 2 μ.

The optical recording medium of this invention can be provided with areflecting layer 3 between the substrate 1 and the organic thin film 2,as shown in FIG. 5. This reflecting layer 3 may be a vapour depositionfilm or laminate film of reflective metal such as aluminum, silver, orchromium.

In the film 2, pits 5 can be formed, as shown in FIG. 6, by irradiationwith a convergent laser beam 4. When depths of the pits 5 are madeequivalent to the thickness of the film 2, an increased reflectance isobtained for the reading laser beam at the pit areas. If a laser beamhaving the same wavelength as the writing laser beam but a lowerintensity is used for reading, the reading beam will be sufficientlyabsorbed at the pit-free areas while highly reflected at the pit areas.Another reading method is to use a laser beam that has a wavelengthdifferent from that of the real-time-writing laser beam highlyabsorbable by the film 2 and will be substantially transmitted by thefilm 2. The reading lasers are responsive to a change in the reflectingphase due to the difference of the film thickness between the pit areasand the pit-free areas.

Recording upon the optical recording medium of this invention can beaccomplished by irradiating it with a gas laser such as the argon laser(wavelength 488 nm), helium-neon laser (wavelength 633 nm), orhelium-cadmium laser (wavelength 442 nm). However, more suitable lasersare those of wavelengths 750 nm and more, particularly those having awavelength in the near infrared region or infrared region, such as thegallium-aluminum-arsenic semiconductor laser. Another method of formingpits is to irradiate the optical recording medium with a light beamincluding rays from various short-pulse emitting lamps such as xenonflash lamps and rays from infrared lamps or to bring a heater intocontact with the recording medium.

Since pit areas of the recording medium are different in reflectancefrom pit-free areas thereof, a track of pits, for instance, is formed byscanning it with electromagnetic radiation and the resulting reflectancedifferences can be read with a photodetector by tracing the track with alow power laser.

The substrate constructing the optical recording medium of thisinvention, if information recording is carried out with a recordinglight beam (electromagnetic wave) incident on the substrate side, isdesired to be transparent to the light beam. A substrate suitable intransparency for the wavelength or spectrum of a given recording lightbeam is desirable for improving the sensitivity, since various recordinglight beams are applicable including, as mentioned above, semiconductorlasers, argon gas laser, helium-neon gas laser, other lasers thewavelengths of which are in the region of visible to infrared rays, andvarious short-pulse emission lamps such as xenon flash lamps.Transparency acceptable of the substrate in this case is such that about90% or more of the incident light is transmittable.

Substrates having adequate transparency to any of the above-mentionedrays of light are films or sheets of, for example, inorganic transparentmaterials such as glass; organic polymers such as polyester,polypropylene, polycarbonates, poly(vinyl chloride), polyamides,polystyrene, and poly(methyl methacrylate); and their modified polymers,copolymers, and blend polymers. When the surface smoothness of thesubstrate itself has a great influence on the S/N ratio as in the caseof video disks, it is desirable to use a substrate coated with theabove-cited polymer by means of a spinner coater or the like.Transparent substrate materials particularly preferred are polyestersand poly(methyl methacrylate).

On the contrary, when a recording light beam is incident on the oppositeside of substrate, it is possible to use substrates, besides saidtransparent substrates, such as films or sheets prepared by adding dyes,pigments, or reinforcing agents to inorganic materials or to organicpolymers and sheets of metals such as aluminum alloys.

According to this invention, the S/N ratio can be improved sufficientlyand in addition a high intensity light beam such as a laser beam can beutilized more efficiently. Further, this invention permits recording byuse of a laser beam having a wavelength of 750 nm or more.

This invention will be illustrated in more detail with reference to thefollowing Examples, wherein parts and percentages are by weight:

EXAMPLE 1

A mixture of 3 parts of the croconic methine dye No. I-(29), 12 parts ofa nitrocellulose solution (methyl ethyl ketone containing 25% of OH-lesslacquer nitrocellulose, mfd. by Daicel Chem. Industries, Ltd.), and 110parts of methyl ethyl ketone was ground in a ball mill for 2 hours. Theresulting dispersion was applied onto a Pyrex glass substrate by dipcoating and was dried at 100° C. for 2 hours to give a recording layerof 0.6 g/m².

The optical recording medium thus prepared was set on a turntable, andwhile rotating the turntable at a speed of 1800 rpm, the recording layerside was irradiated with a 5-mW, 8-MHz gallium-aluminum-arsenicsemiconductor laser (λ 780 nm) converged to a spot size of 1.0 μ, so asto form a spiral track of pits.

Distinct pits were noted as a result of observing the record-bearingsurface of the optical disk with a scanning electron microscope. Thetrack of pits was traced with a low power gallium-aluminum-arsenicsemiconductor laser and the reflected light was detected, giving a wavepattern with a sufficient S/N ratio.

EXAMPLE 2

A solution was prepared by thoroughly mixing 3 parts of the croconicmethine dye No. I-(3) with 10 parts of a nitrocellulose solution (sameas used in Example 1) and 120 parts of methyl Cellosolve. This solutionwas applied onto a Pyrex glass substrate by means of a spinner coater at500 rpm so as to give a dry coating weight of 0.6 g/m². The coating wasdried at 100° C. for 2 hours to form a recording layer. The resultingoptical recording medium was subjected to the same recording and readingtests as in Example 1, giving similar results.

EXAMPLE 3

A molybdenum boat containing 500 mg of the croconic methine dye No.I-(5) and a Pyrex glass substrate were placed in a vacuum chamber, whichwas then evacuated to 1×10⁻⁶ mmHg or less. The dye was heated toevaporate and deposit on the substrate while regulating the heater so asto keep the chamber pressure below 1×10⁻⁵ torr. The optical recordingmedium thus prepared was subjected to the same recording and readingtests as in Example 1, giving similar results.

EXAMPLES 4-7

Optical recording media each comprising a Pyrex substrate and a 0.6 g/m²recording layer were prepared in the same manner as in Example 1 exceptfor using severally the croconic methine dyes Nos. I-(11), I-(14),I-(31), and I-(32) in place of the croconic methine dye No. I-(29).These optical recording media were subjected to the same recording andreading tests as in Example 1, giving similar results.

EXAMPLE 8

An optical recording medium comprising a Pyrex substrate and a recordinglayer vapour-deposited was prepared in the same manner as in Example 3except for using the croconic methine dye No. I-(20) in place of thecroconic methine dye No. I-(5). This optical recording medium wassubjected to the same recording and reading tests as in Example 1,giving similar results.

EXAMPLE 9

A solution was prepared by mixing 3 parts of the thiopyrylium dye No.II-(9), 12 parts of a nitrocellulose solution (same as used in Example1), and 150 parts of tetrahydrofuran. The solution was applied onto aPyrex glass substrate by means of a spinner coater at 500 rpm and wasdried at 100° C. for 2 hours to form a recording layer of 0.7 g/m².

The resulting optical recording medium was set on a turntable, and whilerotating the turntable at a speed of 1800 rpm, the recording layer sidewas irradiated with a 5-mW, 8-MHz gallium-aluminum-arsenic semiconductorlaser (λ 830 nm) converged to a spot size of 0.8 μ, so as to form aspiral track of pits.

Distinct pits were noted as a result of observing the record-bearingsurface of the optical disk with a scanning electron microscope. Thetrack of pits was traced with a low power gallium-aluminum-arsenicsemiconductor laser and the reflected light was detected, giving a wavepattern with a sufficient S/N ratio.

EXAMPLE 10

A solution prepared by thorough mixing of 3 parts of the thiapyryliumdye No. II-(29), 10 parts of a nitrocellulose solution (same as used inExample 1), and 100 parts of monochlorobenzene was applied onto a Pyrexglass substrate by means of a spinner coater at 500 rpm so as to give adry coating weight of 0.6 g/m². The coating was dried at 100° C. for 2hours to form a recording layer. The optical recording medium thusprepared was subjected to the same recording and reading tests as inExample 9, giving similar results.

EXAMPLE 11

A molybdenum boat containing 500 mg of the thiapyrylium dye No. II-(3)and a Pyrex glass substrate were placed in a vacuum chamber, which wasthen evacuated to 1×10⁻⁶ mmHg or less. The dye was heated to evaporateand deposit on the substrate while regulating the heater so as to keepthe chamber pressure below 1×10⁻⁵ torr. The optical recording mediumthus obtained was subjected to the same recording and reading tests asin Example 9, giving similar results.

EXAMPLES 12-20

Optical recording media each comprising a Pyrex substrate and a 0.7 g/m²recording layer were prepared in the same manner as in Example 9 exceptfor using severally the naphthopyrylium dye No. II-(14), pyrylium dyeNo. II-(14), pyrylium dye No. II-(17), naphthothiapyrylium dye No.II-(24), thiapyrylium dye No. II-(30), selenapyrylium dye No. II-(27),thiapyrylium dye No. II-(36), thiapyrylium dye No. II-(38), thiapyryliumdye No. II-(43), and pyrylium dye No. II-(45) in place of thethiapyrylium dye No. II-(9). These optical recording media weresubjected to the same recording and reading tests as in Example 9,giving similar results.

EXAMPLE 21

A solution prepared by mixing 3 parts of the thiapyrylium dye No.III-(18), 12 parts of a nitrocellulose solution (same as used in Example1), and 150 parts of tetrahydrofuran was applied onto a Pyrex glasssubstrate by means of a spinner coater at 500 rpm and was dried at 100°C. for 2 hours to form a recording layer of 0.7 g/m².

The optical recording medium thus prepared was set on a turntable, andwhile rotating the turntable at a speed of 1800 rpm, the recording layerside was irradiated with a 5-mW, 8-MHz gallium-aluminum-arsenicsemiconductor laser (λ 830 nm) converged to a spot size of 0.8 μ, so asto form a spiral track of pits.

Distinct pits were noted as a result of observing the record-bearingsurface of the optical disk with a scanning electron microscope. Thetrack of pits was traced with a low power gallium-aluminum-arsenicsemiconductor laser and the reflected light was detected, giving a wavepattern with a sufficient S/N ratio.

EXAMPLE 22

A solution was prepared by thoroughly mixing 3 parts of thebenzopyrylium dye No. III-(12), 10 parts of a nitrocellulose solution(same as used in Example 1), and 100 parts of monochlorobenzene, and wasapplied onto a Pyrex glass substrate by means a spinner coater at 500rpm so as to give a dry coating weight of 0.6 g/m². The coating wasdried at 100° C. for 2 hours to give a recording layer.

The optical recording medium thus prepared was subjected to the samerecording and reading tests as in Example 21, giving similar results.

EXAMPLE 23

A molybdenum boat containing 500 mg of the thiapyrylium dye No. III-(11)and a Pyrex glass substrate were placed in a vacuum chamber, which wasthen evacuated to 1×10⁻⁶ mmHg or less. The dye was heated to evaporateand deposit on the substrate while regulating the heater to keep thechamber pressure below 1×10⁻⁵ torr. The optical recording medium thusprepared was subjected to the same recording and reading tests as inExample 21, giving similar results.

EXAMPLES 24-27

Optical recording media each comprising a Pyrex substrate and a 0.7 g/m²recording layer were prepared in the same manner as in Example 21 exceptfor using the thiapyrylium dye No. III-(19), benzopyrylium No. III-(14),thiapyrylium dye No. III-(21), and thiapyrylium dye No. III-(22) inplace of the thiapyrylium dye No. III-(18). These recording media weresubjected to the same recording and reading tests as in Example 21,giving similar results.

EXAMPLE 28

A solution was prepared by thoroughly mixing 3 parts of the polymethinedye No. IV-(10), 12 parts of a nitrocellulose solution (same as used inExample 1), and 70 parts of methyl ethyl ketone. The solution wasapplied onto a Pyrex glass substrate by means of a spinner coater andwas dried at 100° C. for 2 hours to form a recording layer of 0.6 g/m².

The optical recording medium thus prepared was set on a turntable, andwhile rotating the turntable at a speed of 1800 rpm, the recording layerside was irradiated with a 5-mW, 8-MHz gallium-aluminum-arsenicsemiconductor laser (λ 780 nm) converged to a spot size of 1.0 μ, so asto form a spiral track of pits.

Distinct pits were noted as a result of observing the record-bearingsurface of the optical disk with a scanning electron microscope. Thetrack of pits was traced with a low power gallium-aluminum-arsenicsemiconductor laser and the reflected light was detected, giving a wavepattern with a sufficient S/N ratio.

EXAMPLES 29-33

Optical recording media each comprising a Pyrex substrate and a 0.6 g/m²recording layer were prepared in the same manner as in Example 28 exceptfor using the polymethine dyes Nos. IV-(3), IV-(11), IV-(17), IV-(22),and IV-(25) in place of the polymethine dye No. IV-(10). These opticalrecording media were subjected to the same recording and reading testsas in Example 28, giving similar results.

EXAMPLE 34

A mixture of 3 parts of the polymethine compound No. V-(3), 12 parts ofa nitrocellulose solution (same as used in Example 1), and 70 parts ofmethyl ethyl ketone was thoroughly mixed in a ball mill. The resultingdispersion was applied by dip coating onto an aluminum layervapour-deposited on a glass plate and was dried to form a recordinglayer of 0.6 g/m².

The optical recording medium thus prepared was set on a turntable, andwhile rotating the turntable at a speed of 1800 rpm, the recording layerside was irradiated with a 5-mW, 8-MHz gallium-aluminum-arsenicsemiconductor laser (λ 780 nm) converged to a spot size of 1.0 μ, so asto form a spiral track of pits.

Distinct pits were noted as a result of observing the record-bearingsurface of the optical disk with a scanning electron microscope. Thetrack of pits was traced with a low power gallium-aluminum-arsenicsemiconductor laser and the reflected light was detected, giving a wavepattern with a sufficient S/N ratio.

EXAMPLES 35-39

Optical recording media each comprising an aluminum-vapour-depositedglass substrate and a recording layer were prepared in the same manneras in Example 34 except that the polymethine compounds Nos. V-(5),V-(10), V-(14), V-(17), and V-(20) were used severally in place of thepolymethine compound No. V-(3) but the coating weight when using thecompound No. V-(14) was made 0.8 g/m². These recording media weresubjected to the same recording and reading tests as in Example 34,giving similar results.

EXAMPLE 40

A molybdenum boat containing 500 mg of the polymethine compound No.V-(1) and an aluminum-vapour-deposited glass plate were placed in avacuum chamber, which was then evacuated to 1×10⁻⁶ mmHg or less. Thecompound was heated to evaporate and deposit to a thickness of 0.2 μ onthe aluminum surface while regulating the heater to keep the chamberpressure below 1×10⁻⁵ mmHg. The optical recording medium thus preparedwas subjected to the same recording and reading tests as in Example 34,giving similar results.

EXAMPLES 41 and 42

Optical recording media each comprising an aluminum-vapour-depositedglass substrate and a 0.2-μ recording layer were prepared in the samemanner as in Example 40 except for using severally the polymethinecompounds Nos. V-(5) and V-(13) in place of the polymethine compound No.V-(1). The optical recording media thus prepared were subjected to thesame recording and reading tests as in Example 34, giving similarresults.

EXAMPLE 43

A mixture of 3 parts of the cyanine compound No. VI-(1), 12 parts of anitrocellulose solution (same as used in Example 1), and 70 parts ofmethyl ethyl ketone was thoroughly mixed in a ball mill. The resultingdispersion was applied by dip coating onto an aluminum layervapour-deposited on a glass plate, and was dried to form a recordinglayer of 0.6 g/m².

The optical recording medium thus prepared was set on a turntable, andwhile rotating the turntable at a speed of 1800 rpm, the recording layerside was irradiated was a 5-mW, 8-MHz gallium-aluminum-arsenicsemiconductor laser (λ 780 nm) converged to a spot size of 1.0 μ, so asto form a spiral track of pits.

Distinct pits were noted as a result of observing the record-bearingsurface of the optical disk with a scanning electron microscope. Thetrack of pits was traced with a low power gallium-aluminum-arsenicsemiconductor laser and the reflected light was detected, giving a wavepattern with a sufficient S/N ratio.

EXAMPLES 44-47

Optical recording media each comprising an aluminum-vapour-depositedglass substrate and a recording layer were prepared in the same manneras in Example 43 except for using the cyanine compounds Nos. VI-(6)(coating weight 0.6 g/m²), VI-(8) (coating weight 0.6 g/m²), VI-(10)(coating weight 0.7 g/m²) and VI-(12) (coating weight 0.8 g/m²) in placeof the cyanine compound No. VI-(1). The same recording and reading testsof these recording media as in Example 43 gave similar results.

EXAMPLE 48

A molybdenum boat containing the cyanine compound No. VI-(6) and analuminum-vapour-deposited glass plate were placed in a vacuum chamber,which was then evacuated to 1×10⁻⁶ mmHg or less. The compound was heatedto evaporate and deposit to a thickness of 0.2 μ on the aluminum surfacewhile regulating the heater to keep the chamber pressure below 1×10⁻⁵mmHg.

The optical recording medium thus prepared was subjected to the samerecording and reading tests as in Example 43, giving similar results.

EXAMPLE 49

A mixture of 3 parts of the cyanine compound No. VII-(1), 12 parts of anitrocellulose solution (same as used in Example 1), and 70 parts ofmethyl ethyl ketone was thoroughly mixed in a ball mill. The resultingdispersion was applied by dip coating onto an aluminum layervapour-deposited on a glass plate and was dried to form a recordinglayer of 0.6 g/m².

The optical recording medium thus prepared was set on a turntable, andwhile rotating the turntable at a speed of 1800 rpm, the recording layerside was irradiated with a 5-mW, 8-MHz gallium-aluminum-arsenicsemiconductor laser (λ 780 nm) converged to a spot size of 1.0 μ, so asto form a spiral track of pits.

Distinct pits were noted as a result of observing the record-bearingsurface of the optical disk with a scanning electron microscope. Thetrack of pits was traced with a low power gallium-aluminum-arsenicsemiconductor laser and the reflected light was detected, giving a wavepattern with a sufficient S/N ratio.

EXAMPLES 50-53

Optical recording media each comprising an aluminum-vapour-depositedglass substrate and a recording layer were prepared in the same manneras in Example 49 except that the cyanine compounds Nos. VII-(6),VII-(7), VII-(12), and VII-(13) were used severally in place of thecyanine compound No. VII-(1) but the coating weight when using thecompound No. VII-(12) was made 0.8 g/m². The recording media weresubjected to the same recording and reading tests as in Example 49,giving similar results.

EXAMPLE 54

A molybdenum boat containing 500 mg of the cyanine compound No. VII-(1)and an aluminum-vapour-deposited glass plate were placed in a vacuumchamber, which was then evacuated to 1×10⁻⁶ mmHg or less. The cyaninecompound was heated to evaporate and deposit to a thickness of 0.2 μ onthe aluminum surface while regulating the heater to keep the chamberpressure below 1×10⁻⁵ mmHg. The optical recording medium thus preparedwas subjected to the same recording and reading tests as in Example 49,giving similar results.

EXAMPLE 55

Three parts of the pyrylium type dye No. VIII-(5) was thoroughlydispersed in a mixture of 12 parts of a nitrocellulose solution (same asused in Example 1) and 70 parts of methyl ethyl ketone. The dispersionwas applied by dip coating onto an aluminum layer vapour-deposited on aglass plate and was dried to form a recording layer of 0.6 g/m².

The optical recording medium thus prepared was set on a turntable, andwhile rotating the turntable at a speed of 1800 rpm, the recording layerside was irradiated with a 5-mW, 8-MHz gallium-aluminum-arsenicsemiconductor laser (λ 780 nm) converged to a spot size of 1.0 μ, so asto form a spiral track of pits.

Distinct pits were noted as a result of observing the record-bearingsurface of the optical disk with a scanning electron microscope. Thetrack of pits was traced with a low power gallium-aluminum-arsenicsemiconductor laser and the reflected light was detected, giving a wavepattern with a sufficient S/N ratio.

EXAMPLE 56

A molybdenum boat containing 500 mg of the pyrylium type dye No.VIII-(7) and an aluminum-vacuum-metallized glass plate were placed in avacuum chamber, which was then evacuated to 1×10⁻⁶ mmHg or less. The dyewas heated to evaporate and deposit to a thickness of 0.2 μ on thealuminum surface while regulating the heater to keep the chamberpressure below 1×10⁻⁵ mmHg.

The optical recording medium thus prepared was subjected to the samerecording and reading tests as in Example 55, giving similar results.

EXAMPLES 57-59

Optical recording media each consisting of an aluminum-vapour-depositedglass substrate and a 0.2 μ recording layer were prepared in the samemanner as in Example 56 but using severally the pyrylium type dyes Nos.VIII-(5), VIII-(13), and VIII-(15) in place of the pyrylium type dye No.VIII-(5).

The same recording and reading tests on these recording media as inExample 55 gave similar results.

EXAMPLE 60

In 100 ml of dichloromethane were dissolved 2.0 g of the pyrylium typecompound No. VIII-(5) and 2.0 g of poly(4,4'-isopropylidenediphenylenecarbonate) with stirring. A precipitate was formed by adding 50 g oftoluene to the solution, and was redissolved by pouring a sufficientamount of dichloromethane into the mixture. The resulting solutionseparated violet-blue crystals on pouring 500 g of n-hexane thereintowith stirring. These crystals were filtered off and recrystallizationthereof was repeated.

Using this co-crystalline complex in place of the compound No. VIII-(5),an optical recording medium was prepared in the same manner as inExample 55. The same recording and reading tests on this recordingmedium as in Example 55 gave similar results.

EXAMPLE 61

A solution of 1.5 parts of the compound No. IX-(1) in a mixture of 12parts of a nitrocellulose solution (same as used in Example 1) and 30parts of dimethylformamide was thoroughly mixed with 125 parts ofcyclohexanone. The resulting mixture was applied by dip coating onto aPyrex glass substrate and was dried at 100° C. for 2 hours to form arecording layer of 0.5 g/m².

The optical recording medium thus prepared was set on a turntable, andwhile rotating the turntable at a speed of 1800 rpm, the recording layerside was irradiated with a 5-mW, 8-MHz gallium-aluminum-arsenicsemiconductor laser (λ 780 nm) converged to a spot size of 1.0 μ, so asto form a spiral track of pits.

Distinct pits were noted as a result of observing the record-bearingsurface of the optical disk with a scanning electron microscope. Thetrack of pits was traced with a low power gallium-aluminum-arsenicsemiconductor laser and the reflected light was detected, giving a wavepattern with a sufficient S/N ratio.

EXAMPLES 62-64

Optical recording media each consisting of a Pyrex glass substrate and a0.5 g/m² recording layer were prepared in the same manner as in Example61 except for using severally the compounds Nos. IX-(2), IX-(4), andIX-(6) in place of the compound No. IX-(1). These recording media weresubjected to the same recording and reading tests as in Example 61,giving similar results.

What is claimed is:
 1. An optical recording process comprisingselectively irradiating an optical recording medium comprising asubstrate and recording layer with a recording light beam to formoptically detectable pits on said recording layer, thereby recordinginformation, said recording layer having a thickness of 10 μ or less andcontaining at least 1% by weight of at least one of the compoundsrepresented by Formulas (1), (2), (9) and (10): ##STR188## wherein R₁₁and R₁₂ are each alkyl, substituted alkyl, cyclic alkyl, alkenyl,aralkyl, substituted aralkyl, aryl, or substituted aryl; Z₁₁ and Z₁₂ areeach nonmetal atomic groups necessary to complete a substituted orunsubstituted heterocyclic ring; a and b are each 0 or 1; M⁺ representsa cation; and X⁻ is an anion; ##STR189## wherein R₁₁ and R₁₂ reachalkyl, substituted alkyl, cyclic alkyl, alkenyl, aralkyl, substitutedaralkyl, aryl, or substituted aryl; Z₁₁ and Z₁₂ are each nonmetal atomicgroups necessary to complete a substituted or unsubstituted heterocyclicring; a and b are each 0 to 1; ##STR190## wherein A₃ is ##STR191## Z₉₃and Z₉₄ are each sulfur, oxygen, or selenium; Z₉₁ is an atomic groupnecessary to complete a pyrylium, thiapyrylium, selenapyrylium,benzopyrylium, naphthothiapyryulium or naphthoselenapyrylium ring whichis substituted or unsubstituted; Z₉₂ is an atomic group necessary tocomplete a pyrane, thiapyrane, selenapyrane, benzopyrane,benzothiapyrane, naphthopyrane, naphthothiapyrane ornaphthoseleneapyrane ring which is substituted or unsubstituted R₉₁,R₉₂, R₉₃, R₉₄ are each alkyl, alkoxyl, or a substituted or unsubstitutedaryl, styryl 4-phenyl-1, 3-butadienyl, or heterocyclic residue, whereR₉₁ coupled with R₉₂ and R₉₃ coupled with R₉₄ can each form asubstituted or unsubstituted benzene ring; and v and w are each 1 or 2;##STR192## wherein R₂₁ and R₂₂ each represent alkyl or R₂₁ and R₂₂together with the nitrogen atom to which they are attached from abenzene ring; R₂₃, R₂₄, R₂₅ and R₂₆ are each hydrogen; halogen, alkylalkoxy, or hydroxyl, where combinations of R₂₄ and combination of R₂₅and R₂₆ can each form a benzene ring.
 2. The recording process of claim1, including employing a laser as said recording light beam.
 3. Therecording process of claim 2, including employing as said recordinglight beam a xenon flash.
 4. The recording process of claim 1, whereinthe recording medium is scanned with a recording light beam along atrack.
 5. The recording process of claim 1, wherein the recording lightbeam irradiates the recording layer side.
 6. The recording process ofclaim 1, wherein the recording light beam irradiates the substrate side.7. The recording process of claim 1, including employing a recordinglayer containing a binder and at least one of the compounds representedby the Formulas (1), (2), (9) and (10).
 8. The recording process ofclaim 7, including employing as said binder at least one member selectedfrom the group consisting of cellulose esters, cellulose ethers, vinyltype resins and copolymers thereof, acrylic resins, polyester resins,polycarbonates and copolyesters thereof, polyarylates, polymides, epoxyresins, phenolic resins and polyolefins.
 9. The recording process ofclaim 7, including employing a cellulose ester as said binder.
 10. Therecording process of claim 7, including employing nitrocellulose as saidbinder.
 11. The recording process of claim 7, including employing anorganic thin film having a dry thickness of 2 μ or less as saidrecording layer.
 12. The recording process of claim 1, includingemploying a reflecting layer between said substrate and said recordinglayer.
 13. The recording process of claim 12 including employing avapor-deposited film or aluminum silver or chromium as said reflectinglayer.
 14. The recording process of claim 12, including employing alaminate film or aluminum, silver or chromium as said reflecting layer.15. The recording process of claim 1, including employing the step offorming the recording layer by vapor depositing a compound representedby one of the Formulas (1), (2), (9) and (10).
 16. The recording processof claim 1, including employing optically-detectable pits.
 17. Theoptical recording process according to claim 1, wherein the content ofthe at least one compound in the recording layer is from 20 to 70% byweight.
 18. The process of claim 1 including the step of illuminatingsaid recording layer with a reading light to detect optical variation ofsaid pits, thereby reading out said recorded information.
 19. Theprocess of claim 18, wherein said recorded information is read out bydetecting the reflection of said reading light from said recordinglayer.
 20. An optical recording process comprising: selectivelyirradiating an optical recording medium comprising a substrate andrecording layer with a recording light beam to form optically detectablepits on said recording layer thereby recording information, saidrecording layer having a thickness of 10 microns or less and containingat least 1% by weight of at least one of the compounds represented byFormula 2: ##STR193## wherein R₁₁ and R₁₂ are each alkyl, substitutedalkyl, cyclic alkyl, alkenyl, aralkyl, substituted aralkyl, aryl, orsubstituted aryl; Z₁₁ and Z₁₂ are each nonmetal atomic groups necessaryto complete a substituted or unsubstituted heterocyclic ring and a and bare each 0 to
 1. 21. An optical recording process comprising:selectively irradiating an optical recording medium comprising asubstrate and a recording layer with a recording light beam to formoptically detectable pits on said recording layer thereby recordinginformation, said recording layer having a thickness of 10 microns orless and containing at least 1% by weight of at least one of thecompounds represented by Formula 1: ##STR194## wherein R₁₁ and R₁₂ areeach alkyl, substituted alkyl, cyclic alkyl, alkenyl, aralkyl,substituted aralkyl, aryl, or substituted aryl; Z₁₁ and Z₁₂ are eachnonmetal atomic groups necessary to complete a substituted orunsubstituted heterocyclic ring; a and b are each 0 or 1; M⁺ representsa cation and X⁻ is an anion.
 22. An optical recording processcomprising: selectively irradiating an optical recording mediumcomprising a substrate and a recording layer with a recording light beamto form optically detectable pits on said recording layer therebyrecording information, said recording layer having a thickness of 10microns or less and containing at least 1% by weight of at least one ofthe compounds represented by Formula 9: ##STR195## wherein A₃ is##STR196## Z₉₃ and Z₉₄ are each sulfur, oxygen or selenium; Z₉₁ is anatomic group necessary to complete a pyrylium, thiapyrylium,selenapyrylium, benzopyrylium, naphthothiapyrylium ornaphthoselenepyrylium ring which is substituted or unsubstituted; Z₉₂ isan atomic group necessary to complete z pyrane, thiapyrane,selenapyrane, benzopyrane, benzothiapyrane, naphthopyrane,naphthothiapyrane or napthoseleneapyrane ring which is substituted orunsubstituted R₉₁, R₉₂, R₉₃, R₉₄ are each alkyl, alkoxy, or asubstituted or unsubstited aryl, styryl, 4-phenyl-1, 3-butyadienyl, orheterocyclic residue, where R₉₁ coupled with R₉₂ and R₉₃ coupled withR₉₄ can each form a substituted or unsubstituted benzene ring; and v andw are each 1 or
 2. 23. An optical recording process comprising:selectively irradiating an optical recording medium comprising asubstrate and a recording layer with a recording light beam to formoptically detectable pits on said recording layer thereby recordinginformation, said recording layer having a thickness of 10 microns orless and containing at least 1% by weight of at least one of thecompounds represented by Formula 10: ##STR197## wherein R₂₁ and R₂₂ eachrepresent alkyl or R₂₁ and R₂₂ together with the nitrogen atom to whichthey are attached from a benzene ring; R₂₃, R₂₄, R₂₅ and R₂₆ are eachhydrogen; halogen, alkyl alkoxy, or hydroxyl, where combinations of R₂₄and combinations of R₂₅ and R₂₆ can each form a benzene ring.